CN101276004A - Protective film, polarizing plate, and liquid crystal display device - Google Patents

Abstract

The present invention provides a protective film which achieves high surface hardness and low moisture permeability, a polarizing plate using the protective film, and a liquid crystal display device having a high surface hardness and excellent durability using the polarizing plate. The protective film of the present invention contains a low moisture-permeable layer and a hard coat layer having an average thickness of 10 mum or more, which are laminated in that order over one surface of a transparent substrate film, and has a moisture permeability at 60 DEG C and 95% relative humidity of 500 g/m<2 >per day or less.

Description

Diaphragm, polaroid and liquid crystal indicator

Background of invention

The present invention relates to a kind of diaphragm of realizing high surface hardness and low moisture permeability, use the polaroid and the liquid crystal indicator of described diaphragm, more specifically relate to a kind of diaphragm with low soak layer and thickness 10 μ m or bigger hard conating, use the polaroid and the liquid crystal indicator of described diaphragm.

Technical field

In liquid crystal indicator (LCD), plasma display (PDP), electroluminescent display (ELD) and CRT display various other liquid crystal indicators such as (CRT), on the surface of display, dispose antireflection film, as be laminated in the anti-dazzle hard conating (being also referred to as antiglare film in this case) on the overlay substrate or be laminated in hard conating and low reflection layer on the overlay substrate, by surface scattering or low surface reflection, prevent that the contrast that the phantom (imageghosting) because of external reflection of light or image causes from reducing.

In recent years, along with the price of LCD TV etc. descends, use the image display device of antireflection film to popularize.Because this trend, antireflection film and the image display device that they are installed just day by day are in the various environment.Especially, they are resembled handles the CRT TV with glass surface, so the danger that the liquid crystal indicator surface is scratched increases.Therefore, the antireflection film that is installed on the liquid crystal indicator outmost surface not only needs to improve desired visuality in the past, and need have high physical strength (mar resistance etc.).

For obtaining higher physical strength; a kind of antireflection film has been proposed; wherein by using solidification compound coating cellulose acylate film, drying and the light solidifying coating that contains light-cured resin and organic solvent, laminated thickness 10 μ m or bigger hard conating (referring to Japanese Patent Application Publication (JP-A) No.2003-227902).

A kind of antiglare film with high surface hardness has also been proposed; it is by solidification compound coating cellulose acylate film, drying and light solidifying coating then with the resin particle, curable resin and the organic solvent that contain mean grain size 6 μ m-15 μ m, the product of the antiglare layer of laminated thickness 15 μ m-35 (referring to JP-A No.2007-041533).

On the other hand, in LCD TV, the structure of employing is that wherein two polaroids place on each side of liquid crystal cells.It is the cellulose acylate film of the bonding agent of polyvinyl alcohol (PVA) in the configuration of the both sides of polaroid that these polaroids often have through principal ingredient, as the diaphragm of polaroid.

In containing the liquid crystal indicator of cellulose acylate film wherein, when this device is used for severe rugged environment for a long time,, exist inconsistent in the image of demonstration owing to temperature or humidity make the change in size of polaroid as the polaroid of diaphragm.As mentioned above, along with popularizing of LCD TV, the possibility that LCD TV is used for severe rugged environment increases, and therefore needs on the one hand to improve at this.

For addressing these problems; proposed by using diaphragm can improve the humidity resistance of polaroid, the low soak layer that wherein contains vinylidene chloride copolymer is arranged on the surface of cellulose acylate film (referring to JP-A No.62-161103 and 2001-215331).

Yet, also do not propose to realize the diaphragm (antireflection film) of high surface hardness and low moisture permeability so far.

A kind of possible method that overcomes the above problems simultaneously is that the above-mentioned two kinds of technology of combination obtain skin hardness and low moisture permeability.Particularly, the method for coming laminated low moisture permeability hard conating by laminated low soak layer that contains vinylidene chloride copolymer and 10 μ m on substrate film or thicker hard conating.

Yet, present inventor's research discloses, and when hardening resin composition that use contains organic solvent was providing laminated thickness 10 μ m on the film of low soak layer of vinylidene chloride copolymer or bigger hard conating, its problem was, moisture permeability rises, and can not obtain low fully moisture permeability.

In addition, present inventor's research discloses, when hardening resin composition that use contains resin particle, curable resin and organic solvent is providing laminated thickness 10 μ m on the film of the low soak layer that contains vinylidene chloride copolymer or bigger anti-dazzle hard conating, except the problem that moisture permeability rises, resin particle finally can move on to away from substrate side, its problem is that it is too high that surface scattering becomes.

Summary of the invention

The objective of the invention is to solve over the problems referred to above of running into, realize following purpose.Particularly, the purpose of this invention is to provide a kind of diaphragm of realizing high surface hardness and low moisture permeability, use the polaroid of described diaphragm and use described polaroid and have high surface hardness and light leaks the liquid crystal indicator that reduces.

For addressing the above problem, the present inventor furthers investigate, and has found following content.Be laminated thick hard conating, must be coated with the thick coating of solidification compound, thereby the coating weight of contained organic solvent must increase in the solidification compound, but organic solvent can advance to hang down in the soak layer thoroughly and the low soak layer of dissolving.In view of this, the present inventor finds, the thickness by hard conating is set to 10 μ m or bigger and behind the laminated hard conating moisture permeability under 60 ℃ and 95% relative humidity is being controlled to be 500g/m ²It or littler, can address the above problem.

The present invention is based on present inventor's above-mentioned discovery, the mode that addresses the above problem is as follows.Particularly, diaphragm of the present invention comprises: the transparent substrates film; At lip-deep low soak layer of described transparent substrates film; With the hard conating on described low soak layer, the average thickness of described hard conating is 10 μ m or bigger, and the moisture permeability of wherein said diaphragm under 60 ℃ and 95% relative humidity is 500g/m ²It or littler.

Polaroid of the present invention comprises the polarizer and is located at least one lip-deep diaphragm of the described polarizer that wherein said diaphragm comprises the transparent substrates film; At lip-deep low soak layer of described transparent substrates film; With the hard conating on described low soak layer, the average thickness of described hard conating is 10 μ m or bigger, and the moisture permeability of wherein said diaphragm under 60 ℃ and 95% relative humidity is 500g/m ²It or littler.

Liquid crystal indicator comprises: liquid crystal cells; And polaroid, described polaroid comprises the polarizer and is located at least one lip-deep diaphragm of the described polarizer that wherein said diaphragm comprises: the transparent substrates film; At lip-deep low soak layer of described transparent substrates film; With the hard conating on described low soak layer, the average thickness of described hard conating is 10 μ m or bigger, and the moisture permeability of wherein said diaphragm under 60 ℃ and 95% relative humidity is 500g/m ²It or littler.

Embodiment

Describe diaphragm of the present invention, polaroid and liquid crystal indicator below in detail.

(diaphragm)

Diaphragm of the present invention contains low soak layer laminated in regular turn on the transparent substrates film and thickness 10 μ m or bigger hard conating at least.A plurality of this hard conatings can be arranged, and in this case, " average thickness " of hard conating refers to the summation of the average thickness of all hard conatings among the present invention.

Can be by the cross section of observing film in the hope of the thickness of each layer.Cross-section is preferably finished by the cross section of using the sem observation film.When hard conating closes when being laminated on the low soak layer, low soak layer and hard conating can be in their mixing at the interface, thereby are difficult to distinguish the interface between low soak layer and the hard conating.In this case, " average thickness " of hard conating refers to behind laminated hard conating the thickness that the average thickness when making up average thickness that low soak layer and hard conating obtain and deduct only laminated low soak layer is tried to achieve among the present invention.

In addition, when hard conating contained particulate, effect of the present invention was good especially.When the solidification compound that contains particulate, curable resin and organic solvent is used for having laminated thickness 10 μ m on the substrate film of low soak layer or bigger hard conating, except the problem that can not obtain fully low moisture permeability, resin particle finally can move on to away from substrate side, and when adding particulate for the realization surface scattering, this uneven distribution of particulate can make surface scattering rise.This also can make the thickness of the layer that contains particulate descend, and does not contain that part of thickness increase of particulate and low soak layer.

For addressing these problems, laminated in regular turn low soak layer in the film that forms, preferably keeps from the interface between transparent substrates film and the low soak layer with containing the hard conating of particulate on a side of transparent substrates film, that part of average thickness that do not contain particulate is 0.3 μ m-3.0 μ m.More preferably above-mentioned thickness is 0.5 μ m-2.5 μ m, and 0.7 μ m-2.0 μ m is particularly preferred.

In the present invention, by using the sem observation cross section to measure as " the no stratum granulosum thickness " that do not contain that part of average thickness of particulate.Concrete measuring method is recorded in (5) the no stratum granulosum thickness in " evaluation of anti-dazzle hard coat film " of " embodiment ".

As required, between transparent substrates film and hard conating, antistatic backing can be set (for example, when needs use when showing that side reduces surface resistance, or when dust on the surface or other local attachings use when becoming problem), bonding improvements layer, interference fringe prevent layer (when the refringence between substrate and the hard conating be 0.03 or use when bigger) etc.As long as these layers are arranged between transparent substrates film and the hard conating, they can be between substrate film and the low soak layer or between low soak layer and hard conating.

In addition, containing one or more layers the anti-reflection layer that is selected from the layer that comprises low-index layer in the hard conating one side setting away from the transparent substrates film is preferred pattern.

Provide the preferred example of layer structure below, but the invention is not restricted to following structure.

Substrate film, low soak layer, hard conating

Substrate film, low soak layer, hard conating, low-index layer

Substrate film, low soak layer, hard conating, high refractive index layer, low-index layer

Substrate film, low soak layer, hard conating, middle index layer, high refractive index layer, low-index layer

Substrate film, low soak layer, anti-dazzle hard conating

Substrate film, low soak layer, anti-dazzle hard conating, low-index layer

The moisture permeability of diaphragm of the present invention under 60 ℃ and 95% relative humidity is preferably 500g/m ²It or littler, more preferably 400g/m ²It or littler, more preferably 300g/m again ²It or littler.

It is 500g/m that moisture permeability is set ²It or more I with the polarization layer generation change in size of the liquid crystal indicator that suppresses to be provided with diaphragm.

In addition, above-mentioned moisture permeability is preferably 50g/m ²It or bigger, more preferably 80g/m ²It or bigger, more preferably 100g/m again ²It or bigger.It is 50g/m that moisture permeability is set ²It or bigger permission discharge moisture effectively in the drying steps of processing polaroid.

Here, the method of measuring above-mentioned moisture permeability can be documented in " Physical Properties ofPolymer[Koubunshi no Bussei] II " (Polymer Experiment Course[KoubunshiJikken Kouza] 4, Kyoritsu Shuppan Co., Ltd.), the method among the pp.285-294: measure steam transit dose (quality method, thermometer method, vapor method, absorption method).With the membrane sample of diameter 70mm conditioning humidity 24 hours under 60 ℃ and 95% relative humidity, according to JIS Z 0208, the amount of moisture (g/m of the calculating per unit surface area of poor quality before and after the conditioning humidity ²).

The moisture permeability of the commercially available cellulose acylate film of measuring by said method is generally 1,400g/m ²My god-1,500g/m ²My god (when thickness 80 μ m under these conditions moisture permeability).

" transparent substrates film "

The transmittance of transparent substrates film is preferably 80% or bigger, and more preferably 86% or bigger.

In the present invention, use spectrophotometer,, try to achieve the transmittance of transparent substrates film by every 1nm and calculating mean value in the wavelength coverage of measuring 380nm-780nm.

The mist degree of transparent substrates film is preferably 2.0% or littler, and more preferably 1.0% or littler.

According to JIS K 6714, use haze meter (HGM-2DP, Suga Test Instruments makes), the mist degree of the optical compensation membrane sample of measuring 40mm * 80mm under 25 ℃ and 60%RH.

The refractive index of transparent substrates film is preferably 1.4-1.7.

Use sodium vapor lamp as light source, use Abbe refractometer (Ltd. makes for DR-1A, Atago Co.), can measure the refractive index of transparent substrates film.

The examples of material of transparent substrates film comprises that cellulose esters, polyamide, polycarbonate, polyester are (as polyethylene terephthalate, PEN, poly--1,4-cyclohexanedimethyleterephthalate terephthalate, tygon-1,2-biphenoxyl ethane-4,4 '-dicarboxylic ester and poly-to the dioctyl phthalate butanediol ester), polystyrene (as syndiotactic polytyrene), polyolefin (as polypropylene, tygon or polymethylpentene), polysulfones, polyethersulfone, poly-allylat thing, polyetherimide, polymethylmethacrylate and polyetherketone.Cellulose esters, polycarbonate, polyethylene terephthalate and PEN are preferred.

[cellulose acylate film]

Cellulose acylate film is preferably used as the transparent substrates film.Make cellulose acylate by esterified cellulose.For example, at least a in refining velveteen, mestha and the paper pulp and as the cellulose before esterification.

-cellulose acylate-

The term that uses among the present invention " cellulose acylate " refers to fatty acid ester of cellulose, and wherein low-grade fatty acid ester is preferred, and the fatty acid ester of cellulose film is particularly preferred.

" lower fatty acid " refers to have 6 or the fatty acid of carbon atom still less.Cellulose acylate with 2-4 carbon atom is preferred, and cellulose ethanoate is particularly preferred.The also preferred fatty acid ester that mixes that uses is as cellulose acetate propionate or cellulose acetate butyrate.

The viscometric degree of polymerization of cellulose acylate (Dp) is preferably 250 or bigger, and more preferably 290 or bigger.

In addition, according to gel permeation chromatography, preferably narrower by the molecular weight distribution of the cellulose acylate of Mw/Mn (wherein Mw is the quality mean molecular weight, and Mn is a number-average molecular weight) indication.Particularly, the Mw/Mn value is preferably 1.0-5.0, more preferably 1.0-3.0, more preferably 1.0-2.0 again.

The cellulose acylate of degree of acetylation 55.0%-62.5% is preferably used as the transparent substrates film.

Degree of acetylation is 57.0%-62.0% more preferably, more more preferably 59.0%-61.5%.

Term " degree of acetylation " refers to the acetate amount that combines with the cellulose of per unit mass.

Can try to achieve degree of acetylation according to the measurements and calculations of the described acidylate degree of ASTM D-817-91 (methods of testing of cellulose acylate etc.).

In cellulose acylate, the hydroxyl in cellulosic 2-, 3-and 6-position is not evenly replaced, and the degree of substitution of 6-position tends to less.

In the cellulose acylate that the present invention uses, the degree of substitution of cellulose 6-position preferably is equal to or greater than the degree of substitution of 2-or 3-position.The ratio that the degree of substitution of 6-position accounts for the total degree of substitution of 2-, 3-and 6-position is preferably 30%-40%, more preferably 31%-40%, more preferably 32%-40% again.

Various adjuvants can be used in the transparent substrates film, with mechanical property of regulating film (as film strength, curl, dimensional stability and sliding) and permanance (as humidity resistance and against weather).The example of adjuvant comprises that plastifier (as the ester of phosphate, phthalic ester and polyvalent alcohol and fatty acid), UV blocking agent (as hydroxy benzophenone compound, benzotriazole cpd, salicylate compound and alpha-cyanoacrylate ester compounds), anti aging dope (as antioxidant, peroxide decomposer, free radical inhibitors, metal passivator, sour trapping agent and amine), particulate are (as SiO ₂, Al ₂O ₃, TiO ₂, BaSO ₄, CaCO ₃, MgCO ₃, talcum and porcelain earth), separant (parting agent), antistatic agent and infrared adsorbent.

The material write up of above-mentioned transparent substrates film is at Japan Institute of Invention andInnovation Technical Disclosure No.2001-1745, pp.17-22 (distribution on March 15 calendar year 2001, JIII) in.

The use amount of above-mentioned adjuvant preferably accounts for 0.01 quality %-20 quality % of transparent support, more preferably 0.05 quality %-10 quality %.

" low soak layer "

The coating that low soak layer is preferably formed by the compound that contains chlorine.In this case, coating preferably has the resin derived from the repetitive of chloride vinyl monomer.The exemplary of chloride vinyl monomer is vinyl chloride and vinylidene chloride.Wherein, vinylidene chloride is particularly preferred.

By making the polymerizable monomer copolymerization together of vinyl chloride or vinylidene chloride, can obtain above-mentioned chloride monomer.

-with the monomer of chloride vinyl monomer copolymerization-

The example of copolymerization monomer comprises the monomer that is selected from olefines, phenylethylene, esters of acrylic acid, methyl acrylic ester, acrylic amide, methacryl amine, itaconate class, maleate class, dimethyl ester class, N-alkyl maleimide class, maleic anhydride class, vinyl cyanide, vinyl ethers, vinyl ester, vinyl ketones, vinyl heterocyclic compound, glycidyl esters class, unsaturated nitrile and unsaturated carboxylic acid class.

The example of olefines comprises bicyclopentadiene, ethene, propylene, 1-butylene, 1-amylene, isoprene, chlorbutadiene, butadiene and 2,3-dimethyl butadiene.

The example of phenylethylene comprises styrene, methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, cumene ethene, 1-chloro-4-methyl-benzene, methoxy styrene, acetoxy-styrene, chlorostyrene, dichlorostyrene, bromstyrol, trifluoromethyl styrene and methyl ethylene benzoic ether.

The object lesson of esters of acrylic acid and methyl acrylic ester comprises methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, the acrylic acid pentyl ester, 2-EHA, 2-ethyl hexyl acrylate, acrylic acid uncle monooctyl ester, acrylic acid 2-methoxyl ethyl ester, acrylic acid 2-butoxy ethyl ester, acrylic acid 2-phenoxy ethyl, acrylic acid chloroethene ester, acrylic acid cyano group ethyl ester, the acrylic acid dimethylamino ethyl ester, benzyl acrylate, the acrylic acid methoxy benzyl ester, acrylic acid chaff ester, phenyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, the methacrylic acid pentyl ester, hexyl methacrylate, methacrylic acid 2-Octyl Nitrite, 2-Propenoic acid, 2-methyl-, octyl ester, benzyl methacrylate, methacrylic acid cyano-acetoxy ethyl ester, methacrylic acid benzyl chloride ester, methacrylic acid sulphur propyl ester, methacrylic acid N-ethyl-N-phenyl amino ethyl ester, methacrylic acid 2-methoxyl ethyl ester, methacrylic acid 2-(3-phenyl propoxyl group) ethyl ester, dimethylaminoethyl acrylate methyl base amino-benzene oxygen ethyl ester, methacrylic acid chaff ester, tetrahydrofurfuryl methacrylate, phenyl methacrylate, the methyl methacrylate phenyl ester, methacrylic acid naphthalene ester, Hydroxyethyl Acrylate, methacrylic acid hydroxyl ethyl ester, the acrylic acid hydroxy propyl ester, methacrylic acid hydroxyl propyl ester, methacrylic acid 3-chloro-2-hydroxy propyl ester, acrylic acid 2,2-dimethyl hydroxyl propyl ester, acrylic acid 5-hydroxyl pentyl ester, single acrylic acid diglycol ester, single acrylic acid trihydroxymethylpropanyl ester, single acrylic acid pentaerythritol ester, 2,2-dimethyl-3-hydroxy propyl methacrylate, the 5-hydroxy propyl methacrylate, monomethyl acrylic acid diglycol ester, monomethyl acrylic acid trihydroxymethylpropanyl ester and monomethyl acrylic acid pentaerythritol ester.

The object lesson of vinyl ethers comprises methyl vinyl ether, butyl vinyl ether, the hexyl vinyl ether, the octyl group vinyl ether, decave, the ethylhexyl vinyl ether, the methoxy ethyl vinyl ether, the ethoxyethyl group vinyl ether, the chloroethyl vinyl ether, 1-methyl-2,2-dimethyl propyl vinyl ether, 2-ethyl-butyl ether, the dimethyl aminoethyl vinyl ether, the diethylamino ethyl vinyl ether, butyl amino-ethyl vinyl ether, benzyl vinyl ether, the tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyltoluene base ether, the vinyl chloride phenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl anthryl ether.

The object lesson of vinyl ester comprises vinyl acetate, propionate, vinyl butyrate, the isobutyric acid vinyl acetate, vinyl-dimethyl base propionic ester, vinyl ethyl butyric acid ester, the valeric acid vinyl acetate, vinyl caproate, vinyl chloroacetate, the dichloroacetic acid vinyl acetate, the methoxyacetic acid vinyl acetate, the butoxy acetic acid vinyl acetate, the vinyl benzene yl acetate, the acetoacetate vinyl acetate, the lactic acid vinyl acetate, vinyl-beta-phenyl butyric ester, vinyl cyclohexane carboxylic acid ester, vinyl benzoate, vinyl salicylate, the chlorobenzoic acid vinyl acetate, tetrachloro-benzoic acid vinyl acetate and naphthoic acid vinyl acetate.

The example of acrylic amide comprises acrylamide, Methacrylamide, ethyl acrylamide, propyl group acrylamide, butyl acrylamide, tert-butyl group acrylamide, cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxy ethyl acrylamide, dimethyl aminoethyl acrylamide, Phenyl Acrylamide, DMAA, diethyl acrylamide, beta-cyano ethyl acrylamide and N-(2-acetoacetoxy groups ethyl) acrylamide.

The example of methacryl amine comprises Methacrylamide, the methyl acrylamide, the ethyl-methyl acrylamide, the propyl methyl acid amides, the butyl methyl acrylamide, tert-butyl group Methacrylamide, the cyclohexyl methyl acrylamide, the benzyl Methacrylamide, the hydroxymethyl Methacrylamide, the methoxy ethyl Methacrylamide, the dimethyl aminoethyl Methacrylamide, the phenyl methyl acrylamide, dimethylmethacryl amide, the diethylmethyl acrylamide, beta-cyano ethyl-methyl acrylamide and N-(2-acetoacetoxy groups ethyl) Methacrylamide.

Acrylic amide with hydroxyl can be used as the copolymerization monomer, its example comprises N-hydroxymethyl-N-(1,1-dimethyl-3-oxo-butyl) acrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N-ethyl-N hydroxymethyl acrylamide, N, N-dihydroxymethyl acrylamide, N-ethanol acrylamide, N-propyl alcohol acrylamide and N hydroxymethyl acrylamide.

The example of itaconic acid diester comprises dimethyl itaconate, diethyl itaconate and dibutyl itaconate.The example of maleic acid diester comprises diethyl maleate, Malaysia dimethyl acid esters and dibutyl maleate.The example of dimethyl ester comprises DEF, dimethyl fumarate and dibutyl fumarate.

The example of above-mentioned vinyl ketones comprises methyl vinyl ketone, phenyl vinyl ketone and methoxy ethyl vinyl ketone.The example of vinyl heterocyclic compound comprises vinylpyridine, N-vinyl imidazole, N-Yi Xi oxazolidinone, N-vinyl triazole and N-vinyl pyrrolidone.The example of ethylene oxidic ester comprises glycidyl acrylate and glycidyl methacrylate.The example of unsaturated nitrile comprises vinyl cyanide and methacrylonitrile.The example of N-alkyl maleimide class comprises N-ethyl maleimide and N-butyl maleimide.

The example of above-mentioned unsaturated carboxylic acid class comprises acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid, also comprises the acid anhydrides of fumaric acid, itaconic acid and maleic acid.Can also use in these copolymerization monomers two or more.

Chlorine-containing polymer described in the present invention has been documented among JP-A No.53-58553,55-43185,57-139109,57-139136,60-235818,61-108650,62-256871,62-280207, the 63-256665 etc.

The ratio of chloride vinyl monomer in chlorine-containing polymer is preferably 50 quality %-99 quality %, more preferably 70 quality %-97 quality %, more preferably 80 quality %-95 quality % again, preferred especially 88 quality %-93 quality %.The ratio of chloride vinyl monomer is remained on 50 quality % or highlyer obtains low moisture permeability, hold it in 99 quality % or lower and add other copolymerization compositions can crystallization control, and owing in all kinds of solvents, have dissolubility but preferred.

Chloride vinyl monomer is vinylidene chloride preferably.

In addition, preferably by the polymerization vinylidene chloride with can form chlorine-containing polymer with the monomer of vinylidene chloride copolymerization.Can preferably include methacrylonitrile with the monomer component of vinylidene chloride copolymerization.With respect to outside the vinylidene chloride can with the monomer component of vinylidene chloride copolymerization, the ratio of methacrylonitrile is preferably 20 quality % or bigger, more preferably 30 quality % or bigger, more preferably 40 quality % or bigger again.

Chlorine-containing polymer preferably can and comprise 40 quality % or vinylidene chloride polymer that the monomer of bigger methacrylonitrile constitutes with the vinylidene chloride copolymerization by one or more of the vinylidene chloride of 88 quality %-93 quality % and 7 quality %-12 quality %.When methacrylonitrile content is 40 quality % or when bigger, can guarantee the dissolubility in solvent, the increase of moisture permeability simultaneously can remain minimum.

The example of chlorine-containing polymer comprises Saran Resin R241C, Saran Resin F216, SaranResin R204, Saran Latex L502, Saran Latex L529B, Saran Latex L536B, SaranLatex L544D, Saran Latex L549B, Saran Latex L551B, Saran Latex L557, Saran Latex L561A, Saran Latex L116A, Saran Latex L411A, Saran LatexL120, Saran Latex L123D, Saran Latex L106C, Saran Latex L131A, SaranLatex L111, Saran Latex L232A and Saran Latex L321B (these are made by Asahi KaseiChemicals Corporation).

Wherein, preferred use can dissolve in organic solvent and formed behind the low soak layer material that is laminated in the low moisture permeability that can keep hanging down soak layer when hanging down soak layer when hard conating is closed.Saran ResinR204 is a kind of vinylidene chloride polymer, and it is the example that satisfies the commercially available chlorine-containing polymer of these requirements.

Therefore, preferred pattern is to use Saran Resin R204 to form low soak layer as principal ingredient.In this case, low soak layer preferably contains 50 quality % or bigger, more preferably 70 quality % or bigger, more preferably 80 quality % or bigger again, preferred especially 90 quality % or bigger Saran ResinR204.

For satisfying these requirements, be preferably 10g-40g 25 ℃ of chlorine-containing polymer amounts of in the 100g cyclohexanone, dissolving, more preferably 15g-40g, more preferably 20g-35g again.

The thickness of low soak layer is preferably 0.1 μ m-10 μ m, more preferably 0.3 μ m-5 μ m, more preferably 0.5 μ m-3 μ m again.Thickness by keeping low soak layer can be kept low moisture permeability, and avoid the problem of curling in above-mentioned scope.

Use inteferometer coating thickness meter (FE-3000, Otsuka Electronics makes) to measure the thickness of low soak layer.

The mist degree of low soak layer is preferably 5% or littler, and more preferably 3% or littler, more more preferably 1% or littler.Ratio between surface mist degree and the internal haze can be set as required, is 1% or littler but particularly preferably be surperficial mist degree.

" hard conating "

Diaphragm of the present invention preferably has hard conating, thereby can give physical strength.

From giving the enough skin hardnesses of film, simultaneously still making its easy processing view, the thickness of hard conating preferably be about 10 μ m-40 μ m, more preferably 12 μ m-35 μ m, more preferably 15 μ m-30 μ m again.

The intensity of the hard conating of measuring according to pencil hardness test is preferably 4H or bigger, more preferably 5H or bigger.

According to the pencil hardness evaluation method of JIS K 5400, use the test pencil of JIS S 6006, pencil hardness is not see abrasive value under the 4.9N load.

Improve the related factor of pencil hardness and comprise the thickness of hard conating, used bonding agent, used filler and condition of cure, describe below.

Preferably by making solidification compound generation cross-linking reaction or polyreaction form hard conating.For example, be coated with the transparent substrates film by using the coating composition that contains curable polyfunctional monomer or multifunctional oligomer, and polyfunctional monomer or multifunctional oligomer generation cross-linking reaction or polyreaction are formed.

The functional group of curable polyfunctional monomer or multifunctional oligomer is polymerism preferably, and polymerism functional group is particularly preferred.The example of polymerism functional group comprises unsaturated polymerization functional group (polymerism unsaturated group), as (methyl) acryloyl group, vinyl, styryl and allyl.Wherein, (methyl) acryloyl group is preferred.

Replace or except the polymerism unsaturated group, bridging property functional group can also be introduced in the bonding agent.The example of bridging property functional group comprises isocyanate group, epoxy radicals, aziridinyl, oxazolinyl, aldehyde radical, carbonyl, diazanyl, carboxyl, methylol and active methylene group.Can also use vinyl sulfonic acid, acid anhydrides, cyanacrylate derivant, melamine, etherificate methylol, ester, carbamate or metal alkoxide for example tetramethoxy-silicane as monomer with cross-linked structure.Also can use the functional group that presents cross-linking properties through decomposition reaction, for example blocked isocyanate base.

Particularly, bridging property functional group needn't show reaction at once, can be to present reactivity because of decomposition.The bonding agent that can have these bridging property functional groups by coating, heating forms cross-linked structure then.

In addition, solidification compound of the present invention can contain particulate.When containing particulate, can reduce the cure shrinkage of hard conating, therefore the cure shrinkage of hard conating can laminatedly thereon not have in the low soak layer of hard conating and produces same distortion, and the favourable outcome of generation is that the increase of moisture permeability descends, and perhaps can reduce to curl.In addition, solidification compound can contain the particulate of giving inner scattering property.

The amount of particulate is preferably 5 quality %-40 quality % in the bonding agent, more preferably 15 quality %-40 quality %, more preferably 20 quality %-35 quality % again.

Be the refractive index of control hard conating, inorganic particle or have the monomer of high index of refraction can be separately or mixing be added in the bonding agent of hard conating.Except the control refractive index, inorganic particle also has the effect that reduces the cure shrinkage that cross-linking reaction causes.

In the present invention, after forming hard conating, the polymkeric substance by formation such as polymerization polyfunctional monomer and/or high refractive index monomers is known as bonding agent, and bonding agent preferably includes the inorganic particle of dispersion.

The mist degree of hard conating changes with the function of giving polaroid protective film.In the time will keeping image definition and reduce surface reflectivity, make on the surface of hard conating or inside when not giving the light scattering function, haze value is low more good more, more specifically, 10% or be preferred more for a short time, 5% or be preferred more for a short time, 2% or be again preferred more for a short time.

On the other hand, except the function of giving physical strength, when by when anti-dazzle function is given in the scattering of hard conating upper surface, surperficial mist degree is preferably 1%-15%, more preferably 2%-10%.

In addition, when the liquid crystal panel pattern that causes for the scattering-in that makes hard conating or colour inhomogeneous, irregularity in brightness, dazzle etc. are difficult to see or widen the visual angle and give function owing to scattering, internal haze value (obtaining by deducting surperficial haze value with total haze value) is preferably 10%-90%, more preferably 15%-70%, more preferably 20%-50% again.

Therefore, the surperficial mist degree of diaphragm of the present invention and internal haze can freely be set according to intended purpose.

About the concave-convex surface shape of hard conating, obtain transparent surface for keeping image definition, for example, and indication surface roughness characteristic, center line average roughness (Ra) is preferably 0.10 μ m or littler.Ra is 0.09 μ m or littler more preferably, more more preferably 0.08 μ m or littler.

In diaphragm of the present invention, the concave-convex surface shape of hard conating is more important than the concave-convex surface shape of diaphragm, by regulating the center line average roughness of hard conating, the center line average roughness of polaroid protective film can be adjusted in the above-mentioned scope.

In order to keep image definition, except regulating surperficial concaveconvex shape, preferably also regulate the image definition that sees through.The image definition that sees through of polaroid transparent protective film is preferably 60% or bigger.The image blurring index that the image definition that sees through normally shows by film is worth greatly more, and the image definition of seeing by film is good more.The transparent image sharpness is preferably 70% or bigger, and more preferably 80% or bigger.

[anti-dazzle hard conating]

When polaroid protective film of the present invention is used on the surface of liquid crystal indicator, can see the reflected image of object on every side from the teeth outwards sometimes, this can reduce the visuality of display image.In order to prevent this point, preferably make hard coating surface have texture and give the light performance of scattering (anti-dazzle performance) from the teeth outwards.

In addition, there are refractive index ratio transparent substrates film height that hangs down soak layer and the situation that produces interference fringe owing to the refringence between low soak layer and the transparent substrates film.For preventing the adverse effect of interference fringe, preferably give light scattering property to visuality.

The method that forms anti-dazzle performance is documented in the following document: in JP-A No.6-16851, wherein have the unglazed type film of micro concavo-convex shape in its surface by laminated formation; In JP-A No.2000-206317, utilized because the cure shrinkage in the ionizing radiation curable resin that ionization radiation irradiation amount difference causes; In JP-A No.2000-338310, wherein by the dry mass ratio that reduces good solvent and semi-transparent resin, thereby make translucent particulate and semi-transparent resin gelation and curing, and on film coated surface, form concaveconvex shape; In JP-A No.2000-275404, wherein by give the concave-convex surface shape from external pressurized; In JP-A No.2005-195819, being separated of taking place when wherein utilizing from the mixed solution of multiple polymers evaporating solvent forms concave-convex surface shape or the like, can use these known methods to realize above-mentioned purpose.

In the preferred structure of the operable antiglare layer of the present invention, contain and to give the bonding agent that is coated with performance firmly, the particulate of giving anti-dazzle performance and solvent as essential composition, and projection that forms by a plurality of agglomeration of particles bodies or the projection by particulate itself, form concaveconvex shape from the teeth outwards.

Antiglare layer preferably provides anti-dazzle simultaneously and is coated with performance firmly.Describe bonding agent and particulate below in detail.

[bonding agent]

Diaphragm of the present invention can form by making curable compound generation cross-linking reaction or polyreaction.Particularly, can be by with containing curable polyfunctional monomer or multifunctional oligomer coating composition coating transparent substrates film as bonding agent, and polyfunctional monomer or multifunctional oligomer generation cross-linking reaction or polyreaction are formed.

The example of polymerism functional group comprises unsaturated polymerization functional group, as (methyl) acryloyl group, vinyl, styryl and allyl.Wherein, (methyl) acryloyl group is preferred.

Object lesson with polyfunctional monomer of polymerizable group comprises (methyl) diester acrylates of alkylene glycol, neopentyl glycol acrylate, 1 for example, 6-hexanediol (methyl) acrylate and propylene glycol two (methyl) acrylate; (methyl) diester acrylates of polyoxyalkylene glycol, for example triethylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate and polypropylene glycol two (methyl) acrylate; (methyl) diester acrylates of polyvalent alcohol, for example pentaerythrite two (methyl) acrylate; With (methyl) diester acrylates of oxirane or propylene oxide adduct, for example 2,2-two { 4-(acryloxy-diethoxy) phenyl } propane, 2,2-two 4-(acryloyl-oxy-poly-propoxyl group) phenyl) propane.

In addition, also preferably use epoxy radicals (methyl) acrylate, carbamate (methyl) acrylate and polyester (methyl) acrylate as the optical polymerism polyfunctional monomer.

Wherein, preferred polyol and (methyl) acrylic acid ester more preferably have the polyfunctional monomer of 3 or more a plurality of (methyl) acryloyl group in each molecule.

Its object lesson comprises: trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, 1,2,4-cyclohexane four (methyl) acrylate, five glycerol tri-acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate, (two) pentaerythritol triacrylate, (two) pentaerythrite five acrylate, (two) pentaerythrite four (methyl) acrylate, (two) pentaerythrite six (methyl) acrylate, tripentaerythritol triacrylate and tripentaerythritol six acrylate.

In this manual, term " (methyl) acrylate ", " (methyl) acrylic acid " and " (methyl) acryloyl group " refer to " acrylate or methacrylate ", " acrylic or methacrylic acid " and " acryloyl group or methacryl " respectively.

Two or more polyfunctional monomers also can mix use.

Can in the presence of thermal free radical initiator or optical free radical initiating agent, carry out the polymerization that these have the monomer of ethylenic unsaturated group by heating or ionization radiation irradiation.

For the polyreaction of polymerism polyfunctional monomer, preferably use Photoepolymerizationinitiater initiater.Optical free radical polymerization initiator and light cationic polymerization initiators are preferred Photoepolymerizationinitiater initiaters, and the light cationic polymerization initiators is particularly preferred.

＜Photoepolymerizationinitiater initiater 〉

The example of optical free radical polymerization initiator comprises acetophenones, benzoin class, Benzophenones, phosphinoxides, ketals, anthraquinone class, thioxanthene ketone, azo-compound, superoxide (JP-A No.2001-139663 etc.), 2,3-dialkyl group dione compounds, disulfide, fluorine amines, fragrant sulfonium class, lophine dimer, salt, borate, active ester, reactive halogen, inorganic complex and Coumarins.

The example of acetophenones comprises 2,2-dimethoxy-acetophenone, 2,2-diethoxy acetophenone, right-dimethyl acetophenone, 1-hydroxyl 3,5-dimethylphenyl ketone, 1-hydroxyl-dimethyl-right-isopropyl phenyl ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-4-methyl mercapto-2-morpholinyl Propiophenone, 2-benzyl-2-dimethylamino-1-(4-morpholine and phenyl)-butanone, 4-phenoxy group dichloroacetophenone and the 4-tert-butyl group-dichloroacetophenone.

The example of benzoin class comprises benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin tosylate, benzoin methyl ether, benzoin ethylether and benzoin isopropyl ether.

The example of Benzophenones comprise benzophenone, hydroxy benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulfide, 2; 4-two chloro benzophenones, 4; 4-two chloro benzophenones, to chloro benzophenone, 4; 4 '-dimethylamino benzophenone (Michler ' s ketone) and 3; 3 '; 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone.

Boratory example comprises Jap.P. (JP-B) No.2,764,769, JP-A No.2002-116539 and Kunz and Martin, and organic borate of record in " Rad Tech ' 98, Proceeding April, pp.19-22 (1998), Chicago ".For example, the compound of paragraph [0022]-[0027] record in the instructions of above-mentioned JP-A No.2002-116539.

In addition, the object lesson of other organoboron compounds comprises the complex compound of organic boron transition-metal coordination of putting down in writing among JP-A No.6-348011,7-128785,7-140589,7-306527 and the 7-292014.Its object lesson comprises the ionic complex that contains the dye of positive ion.

The example of phosphinoxides comprises 2,4,6-trimethylbenzoyl diphenyl phosphine oxide.

The example of active ester comprises 1,2-acetyl caproyl, 1-[4-(thiophenyl)-2-(O-benzoyl oximes)], sulphonic acid ester and ring-type active ester compound.

More specifically, the compound 1-21 that lists among the embodiment of JP-A No.2000-80068 is particularly preferred.

The example of salt comprises aromatic series diazo salt, aromatic series salt compounded of iodine and aromatic series sulfonium salt.

The object lesson of reactive halogen comprises people such as Wakabayashi at Bull.Chem.Soc.Japan, Vol.42, p.2924 (1969); U.S. Patent No. 3,905,815; JP-A No.5-27830; And M.P.Hutt, Journal of Heterocyclic Chemistry, Vol.1 (No.3), the compound, particularly s-triazine of record in 1970, it is with trihalomethyl group replacement De oxazole compound it on.

Preferred example comprises that wherein at least one is single-, two-or the Striazine derivative that closes of the methyl that replaces of three-halogen and s-triazine loops.

These initiating agents can use separately or use as potpourri.

The preferred example of commercially available optical free radical polymerization initiator comprises that the Kayacure of Nippon Kayaku manufacturing is (as DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC and MCA), the Irgacure that Ciba Specialty Chemicals makes is (as 651,184,500,819,907,369,1173,1870,2959,4265 and 4263), the Esacure that Sartomer makes is (as KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150 and TZT) and their combination.

By the polyfunctional monomer of 100 mass parts, the preferable amount of Photoepolymerizationinitiater initiater is 0.1 mass parts-15 mass parts, more preferably 1 mass parts-10 mass parts.

＜light sensitizer 〉

Except Photoepolymerizationinitiater initiater, also can use light sensitizer.The object lesson of light sensitizer can comprise n-butylamine, triethylamine, tri-n-butyl phosphine, Michler ketone and thioxanthones.

In addition, can also be used in combination one or more auxiliary agents, as triazo-compound, thiourea compound or sulfhydryl compound.

The example of commercially available light sensitizer comprises the Kayacure (as DMBI and EPA) that Nippon Kayaku makes.

＜thermal free radical initiator 〉

The example of operable thermal free radical initiator comprises organic and inorganic peroxide, organic azo and diazo-compounds.

More specifically, the example of organic peroxide comprises benzoyl peroxide, halobenzene formoxyl superoxide, lauroyl superoxide, acetyl peroxide, dibutyl superoxide, cumene hydroperoxide and butyl hydroperoxides; The example of inorganic peroxide comprises hydrogen peroxide, ammonium persulfate and potassium peroxide; The example of azo-compound comprises 2,2 '-azoisobutyronitrile, 2,2 '-azo two propionitrile and 1,1 '-azo two cyclohexanenitriles; The example of diazo-compounds comprises diazo aminobenzene and p-nitrophenyl diazo salt.

[particulate]

Particulate can be organic granular or inorganic particle.Organic granular is preferably as particulate, and have high transparent and with the refringence of bonding agent be that the particulate of 0.01-0.3 is particularly preferred.

The example of organic granular comprises poly methyl methacrylate particle (refractive index: 1.49), crosslinked poly-(acrylic acid (acrylic)-styrene) copolymer pellet (refractive index: 1.54), melamine resin particle (refractive index: 1.57), polycarbonate pellets (refractive index: 1.57), granules of polystyrene (refractive index: 1.60), crosslinked granules of polystyrene (refractive index: 1.61), 1.60) and benzoguanamine melamino-formaldehyde particle (refractive index: 1.68) polyvinyl chloride particles (refractive index:.

1.44), alumina particle (refractive index: 1.63), Zirconium oxide particle, titanium dioxide granule and hollow or porous inorganic particulate the example of inorganic particle comprises silica dioxide granule (refractive index:.

In these particulates, preferably use crosslinked granules of polystyrene, crosslinked poly-((methyl) acrylate) particle and crosslinked poly-(acrylic acid-styrene) particle.Can realize internal haze of the present invention, surperficial mist degree and center line average roughness by the refractive index of regulating bonding agent according to the refractive index of the particulate that is selected from these particles.

The refractive index of bonding agent (semi-transparent resin) and translucent particle is preferably 1.45-1.70, more preferably 1.48-1.65.The kind of bonding agent and particulate and ratio can suitably be selected, so that refractive index is adjusted in the above-mentioned scope.Can easily determine how to carry out these selections by experiment in advance.

Here, for example, directly measure or measure beam split reflectance spectrum or beam split ellipsometry, can estimate the refractive index of bonding agent quantitatively by using the Abbe refractometer.Being dispersed in the mixing ratio that has two kinds of solvents of different refractivity because of change by the particulate with equivalent makes in the solvent of variations in refractive index, measure turbidity, and use the Abbe refractometer to measure the refractive index of solvent when minimum turbidity point, thereby measure the refractive index of particulate.

Under the situation of above-mentioned particulate,, can add inorganic filler such as silicon dioxide to prevent sedimentation because they are easy to sedimentation in bonding agent.The addition of inorganic filler is big more, prevents that the particulate sedimentation is effective more, but big more to the adverse effect of the transparency of filming.Therefore, in bonding agent particle diameter 0.5 μ m or littler inorganic filler preferred content less than about 0.1 quality %, thereby can not damage the transparency of filming.

When hard conating is antiglare layer, be used to give the preferably larger-size particle of particulate of anti-dazzle performance.

When particle was too small, they were embedded in antiglare layer inside, were difficult to produce from the teeth outwards concaveconvex shape.In addition, use larger-size particle to make that the light scattering angle is narrower, prevent that literal is fuzzy.

More specifically, the preferred mean grain size of particulate is 4 μ m-15 μ m, more preferably 5 μ m-12 μ m, more preferably 6 μ m-10 μ m again.

Further preferably particle diameter accounts for the 30%-75% of hard conating thickness.

Can also use two or more particulates together with different-grain diameter.Bigger particle is given anti-dazzle performance, and smaller particles reduces surfaceness.

The particulate preferred content accounts for 3 quality %-30 quality % of the total solid of the layer that is added with particulate, more preferably accounts for the total solid 5 quality %-20 quality % of layer.When content during less than 3 quality %, add and do not have required effect, when surpassing 30 quality %, can produce such as problems such as image blurring, external haze and dazzles.

In addition, preferred its density of particulate is 10mg/m ²-1,000mg/m ², more preferably 100mg/m ²-700mg/m ²

The preparation of＜particulate and classification 〉

The example of making the method for particulate comprises suspension polymerization, emulsion polymerization, emulsifier-free emulsion polymerization, dispersin polymerization and seeding polymerization, but can make particulate by any method.

More contents about these manufacture methods, can be referring to the method for for example following document: Experimental Methods for Polymer Synthesis[Koubunshi Gousei no Jikkenhou] (Takayuki Otsu and Masayoshi Kinoshita work, Kagaku Dojin Publishing Company, INC.), p.130 and pp.146-147; Synthetic Polymers[Gousei Koubunshi], Vol.1, pp.246-290; And ibid., Vol.3, pp.1-108, and be documented in JP-B No.2,543,503,3,508,304,2,746,275,3,521,560 and 3,580,320 and JP-A No.10-1561,7-2908,5-297506 and 2002-145919 in method.

About the size distribution of particulate, from the inhomogeneity viewpoint of surface property of control haze value and diffusivity and coating, monodisperse particles is preferred.For example, when size is defined when making coarse particle than mean grain size big 20% or bigger particle, these coarse grained ratios are preferably 1% or littler, and more preferably 0.1% or littler, more more preferably 0.01% or littler.

Classification after preparation or the synthetic reaction is the another kind of effective ways that acquisition has the particle of above-mentioned Size Distribution, divides stage by increasing the classification number of times or strengthening, and can obtain having the particle that preferable particle size distributes.

Preferably carry out classification by air classification, centrifugal classification, classification of sedimentation, filtration classification, static classification etc.

In addition, can use two or more matt particles together with different-grain diameter.Can use matt particle to give anti-dazzle performance, use to have and give other optical characteristics than the matt particle of small particle diameter with greater particle size.For example, when anti-dazzle antireflection film is attached on 133ppi or the bigger high-resolution display device, may be known as the image quality defective of " dazzle ".

Dazzle is to cause owing to the concaveconvex shape that exists on the anti-dazzle antireflection film surface makes pixel enlarge or dwindle, and loses brightness uniformity.By using particle diameter ratio to give the matt particle that the matt particle of anti-dazzle performance is little and have the refractive index that is different from bonding agent simultaneously, can alleviate dazzle largely.

Matt particle grain size distribution is measured by the Coulter counter method, and the distribution that will measure changes into the amounts of particles distribution.

[solvent of hard conating]

Common situation is that hard conating is coated on the low soak layer as wet coating, so the solvent that uses in the coating composition is the factor of particular importance.Requirement to solvent is fully to dissolve above-mentioned semi-transparent resin and various other solutes, and does not dissolve above-mentioned translucent particulate, and produces even property of less crawling or the even property of uneven drying in coating and drying steps.

The solubleness that other preferred characteristics are lower floors not too high (this be prevent necessary), and reverse dissolution or swelling coating (this is that excellent bonds is necessary) etc. as small as possible such as albefaction or problem such as loss flatness etc.

Solvent can use separately, but particularly preferred two or more solvents that are to use, and regulates solubleness, drying property and the particle agglomeration etc. of coating solubleness and swelling, material.In addition, by to greatly not adding the solvent that has high swelling property on a small quantity in the main solvent of swelling coating, can improve bonding to coating, and can adverse effect not arranged other performance or condition.

The object lesson of the preferred solvent that uses comprises various ketone (as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone), various ester (as methyl acetate and ethyl acetate) and various cellosolve (as ethyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether).

In addition, preferably use various alcohol (as propylene glycol, ethylene glycol, ethanol, methyl alcohol, isopropyl alcohol, 1-butanols and 2-butanols) and toluene etc.

[high refractive index layer (middle index layer)]

On diaphragm of the present invention,, can further strengthen antireflection type performance on hard conating by high refractive index layer and middle index layer and the utilization optical interference with low-index layer (aftermentioned) is provided

In the following description, high refractive index layer and middle index layer can be referred to as sometimes and make high refractive index layer.In the present invention, used term in high refractive index layer, middle index layer and the low-index layer " height ", " in " and " low " relative size of the refractive index of presentation layer.In addition, about the relation of these layers with transparent substrates, preferably the refractive index of transparent substrates film is greater than the refractive index of low-index layer, and the refractive index of transparent substrates film is less than the refractive index of high refractive index layer.

In this manual, high refractive index layer, middle index layer and low-index layer can be referred to as sometimes and make anti-reflection layer.

For forming low-index layer on high refractive index layer, thereby make antireflection film, the preferred refractive index of high refractive index layer is 1.55-2.40, more preferably 1.60-2.20, more preferably 1.65-2.10, most preferably 1.80-2.00 again.

When being coated with the transparent substrates film with the manufacturing antireflection film with coating, hard conating, middle index layer, high refractive index layer and low-index layer in regular turn, the preferred refractive index of high refractive index layer is 1.65-2.40, more preferably 1.70-2.20.The refractive index of index layer in the adjusting is the value between the refractive index of the refractive index of low-index layer and high refractive index layer.The refractive index of middle index layer is preferably 1.55-1.80.

The object lesson of the inorganic particle that uses in high refractive index layer and the middle index layer comprises TiO ₂, ZrO ₂, Al ₂O ₃, In ₂O ₃, ZnO, SnO ₂, Sb ₂O ₃, ITO and SiO ₂Wherein, TiO ₂And ZrO ₂Owing to can obtain high index of refraction but particularly preferred.

Silane coupled processing or titanium coupling processing are preferably carried out in the surface of above-mentioned inorganic filler, and preferred use have can with the surface conditioning agent of the functional group of adhesive reaction on the filling surface.

By the quality of high refractive index layer, the amount of inorganic particle is preferably 10 quality %-90 quality % in the high refractive index layer, more preferably 15 quality %-80 quality %, more preferably 15 quality %-75 quality % again.In high refractive index layer, can use two or more inorganic particles together.

If low-refraction is placed on the high refractive index layer, the refractive index that preferably is higher than the transparent substrates film of high refractive index layer refractive index so.

By bonding agent crosslinked or that polyreaction obtains, as contain aromatic ring ionising radiation curable compound, contain the ionising radiation curable compound of the halogen atom (as bromine, iodine or chlorine) outside the fluorine or contain ionising radiation curable compound such as sulphur, nitrogen or phosphorus atoms, can be preferred in the high refractive index layer.

Can suitably design the thickness of high refractive index layer according to purposes.When high refractive index layer when the aftermentioned optical interference layer, the thickness of high refractive index layer is preferably 30nm-200nm, more preferably 50nm-170nm, more preferably 60nm-150nm again.

When high refractive index layer does not contain anyly when giving the particle of anti-dazzle function, the mist degree of high refractive index layer is preferably low as far as possible.For example, mist degree is preferably 5% or littler, and more preferably 3% or littler, more more preferably 1% or littler.High refractive index layer preferably is formed on the transparent substrates film by another layer.

When polaroid protective film of the present invention is used on the surface of liquid crystal indicator, on the surface of hard conating, forms low-index layer and help preventing phantom.The following describes the low-index layer that the present invention preferably uses.

[low-index layer]

Be to contain the fluorine atom of 35 quality %-80 quality % and contain bridging property or the thermosetting of the fluorochemicals of polymerism functional group and/or Photocurable composition formation low-index layer preferably by the coating principal ingredient.

The refractive index of the low-index layer in the above-mentioned anti-dazzle antireflection film is preferably 1.45 or littler, more preferably 1.30-1.40, more preferably 1.33-1.37 again.

For reducing refractive index, low-index layer preferably satisfies following formula 3.

1/4 * 0.7 * λ＜n1 * d1＜1/4 * 1.3 * λ formula 3

Wherein n1 is the refractive index of low-index layer, and d1 is the thickness (nm) of low-index layer.In addition, n1 is the value of measuring in the 500-550nm wavelength coverage.

The optical thickness that formula 3 expression, the refractive index of low-index layer and the product of its thickness are represented approaches 1/4 wavelength of 500-550nm, and 500-550nm is the optical wavelength range of high luminous efficiency.

As the value that formula 3 obtains, the thickness of low-index layer is 70-120nm preferably.

Low-index layer for example is to be the solidification compound of fluorochemicals, the cured film that forms of dry and solidified coating then by the coating principal ingredient.

Form the solidification compound that uses in the low-index layer and preferably contain (A) fluorochemicals, (B) inorganic particle and (C) two or more in the organic silane compound particularly preferably are and contain these three kinds simultaneously.

Have the fluoropolymer of low-refraction or fluorine-containing sol-gel material etc. and be preferably used as fluorochemicals.

Fluoropolymer or fluorine-containing sol-gel preferably can be by the materials of heat or crosslinking by ionizing radiation, and its kinetic friction coefficient of surface of the low-index layer that forms is 0.03-0.30, with the contact angle of water be 85 °-120 °.The following describes the material that forms low-index layer.

The fluoropolymer that＜low-index layer is used 〉

The kinetic friction coefficient that fluoropolymer make to solidify caudacoria is 0.03-0.20, with the contact angle of water be 90 °-120 °, pure water landing angle (slipping angle) is 70 ° or littler.Preferably can be by the polymkeric substance of heat or crosslinking by ionizing radiation, because when being coated with the yardage roll film and solidify in tablet is carried, productivity is higher.

In addition, under antiglare film or anti-dazzle antireflection film are attached to situation on the liquid crystal indicator, owing to use the peeling force of commercially available adhesive strip lower, and can after applying, more easily peel off strip of paper used for sealing or label, therefore peeling force is preferably 500gf (4.9N) or littler, more preferably 300gf (2.9N) or littler, more preferably 100gf (0.98N) or littler again.In addition, the surface becomes and more is difficult to scratch, because the skin hardness of measuring by micro Vickers hardness meter is higher, so skin hardness is preferably 0.3GPa or bigger, more preferably 0.5GPa or bigger.

The fluoropolymer that uses in the low-index layer preferably contains 35 quality %-80 quality % fluorine atoms and contains the fluoropolymer of bridging property or polymerism functional group.Its example comprises that hydrolysate, its dehydration condensation and the structural unit of the silane compound (for example, (17 fluoro-1,1,2,2-tetrahydrochysene decyl) triethoxysilane) that contains perfluoroalkyl are the fluoropolymers of fluorine-containing monomer unit and bridging property unit.Under the situation of fluorinated copolymer, main chain preferably only is made of carbon atom.That is, in main chain backbone, preferably there are not oxygen atom or nitrogen-atoms etc.

The object lesson of fluorine-containing monomer unit comprises that fluoroolefins (for example, fluorothene, vinylidene fluoride, tetrafluoroethene, perfluoro capryl ethene, hexafluoropropylene and perfluor-2,2-dimethyl-1,3-dioxole), (methyl) acrylic acid partially or completely fluorinated alkyl ester derivant (as Viscoat 6FM (OsakaOrganic Chemical Industry manufacturing) and M-2020 (Daikin Industries manufacturing)) and the vinyl ether fluoridized wholly or in part.Wherein, preferred perfluoroolefine, and consider refractive index, solubleness, transparency and be easy to acquired, more preferably hexafluoropropylene.

The example of bridging property unit comprises the structural unit that obtains by the monomer that has had self-crosslinking functional group in the polymerizable molecular, and described monomer for example is (methyl) glycidyl acrylate and glycidyl vinyl ether; Introducing has carboxyl by polymerization as (methyl) acryloyl group with crosslinkable groups by polymer reaction; hydroxyl; (described monomer for example is (methyl) acrylic acid to the structural unit that the monomer of amino or sulfo group etc. obtains; (methyl) acrylic acid hydroxyl methyl esters; (methyl) acrylic acid hydroxyl alkane ester; allyl acrylate; the hydroxyethyl vinyl ether; hydroxy butyl vinyl ether; maleic acid or crotonic acid) in and the structural unit (for example can introduce described group) that obtains by making acryloyl chloride and hydroxyl effect.

In order to improve solubleness in solvent and transparency of film etc., except above-mentioned fluorine-containing monomer unit and bridging property unit, as required by copolymerization not the monomer of contain fluorine atoms also can introduce other polymerized units.

Operable other monomeric units are not particularly limited, its example comprises that olefines (for example, ethene, propylene, isoprene, vinyl chloride and vinylidene chloride), esters of acrylic acid (for example, methyl acrylate, ethyl acrylate, 2-EHA), methyl acrylic ester (for example, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, Ethylene glycol dimethacrylate), styrene derivative (for example, styrene, divinylbenzene, vinyltoluene and α-Jia Jibenyixi), vinyl ethers (for example, methyl vinyl ether, ethyl vinyl ether and cyclohexyl vinyl ether), vinyl esters (for example, vinyl acetate, propionate and vinyl cinnamate), acrylic amide (for example, N tert butyl acrylamide and N-cyclohexyl acrylamide), methacryl amine and acrylic nitrile derivates.

As required, hardening agent can be mixed use with fluoropolymer, described in JP-A No.10-25388 and 10-147739.

The useful especially fluoropolymer of the present invention is the random copolymers of perfluoroolefine and vinyl ether or vinyl esters.

Particularly preferably be, it itself is the group (for example, free-radical polymerised group, as (methyl) acryloyl group or ring-opening polymerization group, for example epoxy radicals and oxa-cyclobutyl (oxetanyl group)) of bridging property that this polymkeric substance has.

The polymerized unit that contains crosslinkable groups preferably accounts for the 5mol%-70mol% of the total polymerization unit of polymkeric substance, more preferably 30mol%-60mol%.

The preferred structure of the fluoropolymer that low-index layer is used is the multipolymer of following general formula 2 expressions.

General formula 2

The fine inorganic particle that＜low-index layer is used 〉

The addition of fine inorganic particle is preferably 1mg/m ²-100mg/m ², more preferably 5mg/m ²-80mg/m ², more preferably 10mg/m again ²-60mg/m ²If addition is too little, the improvement of mar resistance is lower, if and addition is excessive, on the surface of low-index layer, can form fine concavo-convex, this will have adverse effect to outward appearance (for example blackstreak) and integrated reflectivity (integrated reflectivity), and therefore preferred addition is in above-mentioned scope.

Because fine inorganic particle is included in the low-index layer, so fine inorganic particle preferably has low-refraction.The example of this particulate comprises magnesium fluoride and Si oxide (silicon dioxide) particulate.Consider refractive index, dispersion stabilization and cost, preferred especially fine particles of silica.

The mean grain size of fine inorganic particle for example is the 10%-100% of low-refraction layer thickness, preferred 30%-100%, more preferably 35%-80%, more preferably 40%-60% again.That is, when the thickness of low-index layer was 100nm, the particle diameter of fine particles of silica is 30nm-100nm preferably, more preferably 35nm-80nm, more preferably 40nm-60nm again.

If fine inorganic particle is too little, the effect that improves mar resistance is lower, and if too big, on the surface of low-index layer, can form fine concavo-convex, this will have adverse effect to outward appearance (for example blackstreak) or integrated reflectivity, and therefore preferred addition is in above-mentioned scope.

Fine inorganic particle can be crystallization or unbodied, can be monodisperse particles or can be the particle of agglomeration, as long as satisfy the particle diameter requirement.Although its optimum shape is spherical, even amorphous, also no problem.

The mean grain size of fine inorganic particle refers to the mean grain size according to Coulter counter mensuration.

For the increase of the refractive index that further minimizes low-index layer, fine inorganic particle preferably has hollow structure, and the refractive index of fine inorganic particle is preferably 1.17-1.40, more preferably 1.17-1.35, more preferably 1.17-1.30 again.Refractive index used herein is meant the refractive index of particle integral body, rather than refers to only refer to the refractive index of the inorganic material of shell when fine inorganic particle has hollow structure.At this moment, suppose that the radius in space in the particle is a, the radius of particle shell is b, and voidage x is by following formula 4 representatives so.

X=(4 π a ³/ 3)/(4 π b ³/ 3) * 100 formula 4

Voidage x is 10%-60% preferably, more preferably 20%-60%, more preferably 30%-60% again.

If the hollow inorganic particulate has lower refractive index and the voidage of Geng Gao, therefore the thickness attenuation of shell and the weakened of particle, consider mar resistance so, and low-refraction can not use less than 1.17 low-refraction particle.

Can use Abbe refractometer (Atago Co., Ltd. makes) to measure the refractive index of fine inorganic particle.

In addition, at least a mean grain size can be mixed use less than 25% fine inorganic particle (being referred to as " small particle diameter fine inorganic particle ") of the thickness of low-index layer with the fine inorganic particle with above-mentioned preferable range particle diameter (being referred to as " big particle diameter fine inorganic particle ").

The small particle diameter fine inorganic particle may reside in the space between the big particle diameter fine inorganic particle, therefore can be as the retention agent of big particle diameter fine inorganic particle.

If low-index layer is that 100nm is thick, the mean grain size of small particle diameter fine inorganic particle is preferably 1nm-20nm so, more preferably 5nm-15nm, more preferably 10nm-15nm again.Consider raw materials cost and retention agent effect, preferably use this fine inorganic particle.

As mentioned above, especially preferably use mean grain size as the 30%-100% of low-refraction layer thickness, have hollow structure, refractive index fine inorganic particle as 1.17-1.40.

In order in dispersion or coating fluid, to realize dispersion stabilization or enhancing affinity and associativity to adhesive ingredients, inorganic particle can carry out physical surface treatment, for example plasma discharge processing or Corona discharge Treatment or carry out chemical surface treatment with surfactant or coupling agent etc.Especially preferably use coupling agent.

Alkoxide compound (for example, titanium coupling agent or silane coupling agent) is preferably used as coupling agent.Silane coupled processing is effective especially.

Coupling agent carries out the surface-treated surface conditioning agent as the fine inorganic particle to low-index layer before the coating fluid of preparation low-index layer.Yet coupling agent preferably also is added in this layer when preparing the coating fluid of low-index layer as adjuvant.

Preferably fine inorganic particle was distributed to before surface treatment in the medium to reduce the surface-treated burden.

The following describes organic silane compound (C).

The organic silane compound that＜low-index layer is used 〉

Viewpoint from mar resistance, particularly from obtaining the viewpoint of antireflection property and mar resistance simultaneously, preferably, one or more that contain in the solidification compound in the partial condensate of hydrolysate of the hydrolysate that is selected from organic silane compound, organosilane and organosilane are planted compounds (reaction solution that obtains is called " colloidal sol component " below sometimes).

When the coating solidification compound, then in drying and heating steps during condensation, these compounds are by forming the bonding agent of curing materials as low-index layer.In addition, in the present invention, because above-mentioned fluoropolymer as fluorochemicals, therefore forms the bonding agent with three-dimensional structure through the active ray irradiation.

Organic silane compound is preferably by following general formula 4 representatives.

General formula 4

Wherein, R ¹⁰Be replacement or unsubstituted alkyl or replacement or unsubstituted aryl.The example of alkyl comprises methyl, ethyl, propyl group, isopropyl, hexyl, decyl and cetyl.

Alkyl preferably has 1-30 carbon atom, more preferably 1-16 carbon atom, more preferably 1-6 carbon atom again.The example of aryl comprises phenyl and naphthyl, preferred phenyl.

X is hydroxyl or hydrolyzable group, and its example comprises alkoxy (alkoxy that preferably has 1-5 carbon atom is as methoxy or ethoxy), halogen atom (as Cl, Br or I) and R ²COO (R wherein ²Hydrogen atom or have the alkyl of 1-5 carbon atom preferably, its example comprises CH ₃COO and C ₂H ₅COO).Wherein, alkoxy is preferred, and is particularly preferred in methoxyl and the ethoxy.

M is the integer of 1-3, preferred 1 or 2, more preferably 1.

As a plurality of R ¹⁰Or during X, these a plurality of R ¹⁰Or X can be identical or different.

R ¹⁰In contained substituting group be not particularly limited.Its example comprises that halogen atom (for example; fluorine; chlorine and bromine); hydroxyl; sulfydryl; carboxyl; epoxy radicals; alkyl (for example; methyl; ethyl; isopropyl; the propyl group and the tert-butyl group); aryl (for example; phenyl and naphthyl); fragrant heterocyclic radical (for example; furyl; pyrazolyl and pyridine radicals); alkoxy (for example; methoxyl; ethoxy; isopropoxy and own oxygen base); aryloxy group (for example; phenoxy group); alkylthio group (for example; methyl mercapto and ethylmercapto group); arylthio (for example; thiophenyl); thiazolinyl (for example; vinyl and 1-propenyl); acyloxy (for example; acetoxyl group; acryloxy and methacryloxy); alkoxy carbonyl (for example; methoxycarbonyl and ethoxy carbonyl); aryloxycarbonyl (for example; phenyloxycarbonyl); carbamyl (for example; carbamyl; N-methylamino formoxyl; N; N-formyl-dimethylamino and N-methyl-N-octyl group carbamyl) and acyl amino (for example, acetyl-amino; benzoyl-amido; amino and the methacryl amino of acryloyl group).These substituting groups can also further be replaced.

As a plurality of R ¹⁰The time, the alkyl that at least one preferably replaces or the aryl of replacement.

[formation of layer]

By being coated with the transparent substrates film with coating fluid, heating and dry coating, solidify curable resin or the monomer that is used to form each layer with rayed and/or heating as required then, form the coating and hard conating as required, low-index layer and other layers that use among the present invention.Form each layer like this.

Method for coating each layer of film of the present invention is not particularly limited, can use any known method, as dip-coating method, airblade coating method, curtain formula curtain coating, rolling method, metal bar rubbing method, intaglio plate rubbing method, extrusion coated method (mould is coated with method) (referring to U.S. Patent No. 2,681,294) or nick version rubbing method.Wherein, for the high productivity feed membrane, it is preferred that nick version rubbing method and mould are coated with method, and it is particularly preferred that mould is coated with method.

Preferably carry out drying under certain condition, make that the organic solvent concentration in the liquid film of dry back coating is 5 quality % or littler, more preferably 2 quality % or littler, more preferably 1 quality % or littler again.

Drying condition is influenced by the hot strength of substrate and the length of transporting velocity and drying steps etc., but the content of organic solvent is preferably low as far as possible, to prevent bonding and to obtain required film hardness.When not containing organic solvent, can omit drying steps, and after coating, shine layer with ultraviolet ray immediately.

Can heat treated coating of the present invention to improve its crystallinity.Heat treatment temperature is preferably 40 ℃-130 ℃, can determine heat treatment time aptly by crystallization degree as required, often is about 5 minutes-48 hours.

In addition, as required, can carry out surface treatment to the one or both sides of transparent substrates film, to improve bonding between transparent substrates film and the coating by oxidizing process or concavo-convexization method etc.The example of oxidizing process comprises that Corona discharge Treatment, glow discharge processing, chromic acid are handled (wetting), flame treatment, hot blast is handled and ozone/ultraviolet treatment with irradiation.

[saponification processing]

When diaphragm of the present invention is used for liquid crystal indicator, for example, be placed on the outmost surface of display device by bonding coat being set in a side.If transparent support is a tri acetyl cellulose, so because tri acetyl cellulose is used as the diaphragm of the polarization layer of protection polaroid, therefore diaphragm of the present invention is preferred directly as polaroid protective film, to reduce cost.

If for example by pressure-sensitive adhesive layer being set in a side; diaphragm of the present invention is placed on the outmost surface of display device; or directly as polaroid protective film, on transparent support, preferably carry out saponification after the formation outermost layer so and handle, to guarantee the bonding of satisfaction.Can carry out saponification by any known method and handle, film be flooded the suitable long time in aqueous slkali as passing through.After film was flooded in aqueous slkali, preferred water fully washed film or floods with the neutralization bases composition in diluted acid, makes and no longer leave the alkali composition in film.

Carrying out the result that saponification handles is, has transparent support surface on the opposite side of that side of outermost layer by hydrophiling.

Has improved especially effectively with principal ingredient on hydrophiling surface is deflection film (deflecting film) bonding of polyvinyl alcohol (PVA).In addition, dust in air is not easy to attach on the hydrophiling surface, thereby in the process of fitting with the deflection film, less dust falls into the space between deflection film and the diaphragm, has prevented the point defect that dust causes so effectively.

Preferably carry out saponification and handle, make that the contact angle with transparent support surface and water on that side opposite side of outermost layer is 40 ° or littler, more preferably 30 ° or littler, more preferably 20 ° or littler again.

The concrete grammar of alkali soap processing can be selected from following two kinds of methods 1 and 2.The advantage of method 1 is; can handle by the process identical with common tri acetyl cellulose film; but because the saponification meeting extends on the surface with optical function always; therefore possible problem is because the basic hydrolysis on surface makes the film deterioration, and perhaps saponification Treatment Solution may be residual and the generation spot.When these problems occurring, method 2 is preferred, even attached special steps.

Method 1: after forming optical functional layer on the transparent support, in aqueous slkali, flood support at least once, thus the back side of saponification film.

Method 2: before or after forming optical functional layer on the transparent support, aqueous slkali is applied to the opposite side of that side of formation optical functional layer of diaphragm, heats support then, wash with water and/or neutralize, thus the back side of saponification film only.

The following describes diaphragm of the present invention as the polaroid of polaroid protective film and the liquid crystal indicator of this polaroid of use.

(polaroid)

Polaroid mainly is made of the polarizer (polarizing coating) and two diaphragms clamping the polarizing coating two sides.Diaphragm of the present invention is preferred for clamping at least one in two diaphragms on polarizing coating two sides.Because diaphragm of the present invention also as polaroid protective film, therefore can reduce the manufacturing cost of polaroid.In addition, the diaphragm of the application of the invention is as outermost layer, can obtain preventing excellent polaroids such as phantom that ambient light etc. produces and mar resistance.

The example of polarizing coating comprises that iodine is that polarizing coating, the dyestuff that uses dichroic dye are that polarizing coating and polyenoid are polarizing coating.Usually using polyvinyl alcohol film to make iodine is that polarizing coating and dyestuff are polarizing coating.

In two diaphragms of the polarizer, the film outside the polaroid protective film of the present invention preferably has the optical compensation films of the optical compensating layer that comprises optical anisotropic layer.Optical compensation films (phase retardation film) can improve the viewing angle characteristic of LCD Panel.

When polaroid of the present invention is used in liquid crystal indicator etc. and goes up, preferably place on the observation side of opposite side of liquid crystal cells.

(liquid crystal indicator)

Diaphragm of the present invention and polaroid can be advantageously used in the image display device, as liquid crystal indicator, and are preferably used as the outermost layer of display.

Liquid crystal indicator has liquid crystal cells and places two polaroids of its both sides, and liquid crystal cells contains liquid crystal in two electrode substrate.In some cases, optical anisotropic layer can place between liquid crystal cells and the polaroid, two optical anisotropic layers perhaps can be set between liquid crystal cells and each polaroid.

Liquid crystal cells is TN (twisted-nematic) pattern, VA (vertical orientated) pattern, OCB (optical compensation curved) pattern, IPS (switching in the face) pattern preferably, or ECB (electrically conerolled birefringence) pattern.

＜TN pattern 〉

In the liquid crystal cells of TN pattern, when not applying voltage, the rod shaped liquid crystal molecule is horizontal alignment basically, and 60-120 ° of arrangement of distortion.

The liquid crystal cells of TN pattern is most frequently used in the colored TFT liquid crystal indicator and is disclosed in many documents.

＜VA pattern 〉

In the liquid crystal cells of VA pattern, the rod shaped liquid crystal molecule is vertical orientated basically when not applying voltage.

The liquid crystal cells of VA pattern comprises: the VA mode liquid crystal unit of (1) narrow sense, and wherein the rod shaped liquid crystal molecule is vertical orientated basically when not applying voltage, but substantial horizontal is orientated (referring to JP-A No.2-176625) when applying voltage; (2) be used to enlarge the liquid crystal cells (referring to SID 97, Digest of Tech.Papers, 28 (Preprint) (1997), 845) of the multiple domain VA pattern (MVA pattern) at visual angle; (3) liquid crystal cells of following pattern (n-ASM pattern), wherein the rod shaped liquid crystal molecule perpendicular is orientated when not applying voltage, but when applying voltage, be orientated to reverse the multiple domain mode (referring to Preprints ofLiquid Crystal Forum of Japan[Nihon Ekishou Touronkai], 58-59 (1998); And the liquid crystal cells of (4) SURVAIVAL pattern (in LCD International 98, reporting).

＜ocb mode 〉

The liquid crystal cells of ocb mode is a kind of liquid crystal cells of curved orientation pattern, and wherein the rod shaped liquid crystal molecule substantial reverse in the upper and lower of liquid crystal cells is orientated (symmetry), and United States Patent (USP) 4,583 discloses this point in 825 and 5,410,422.Because the rod shaped liquid crystal molecule symmetric orientation in the upper and lower of liquid crystal cells, therefore the liquid crystal cells of this curved orientation pattern has optics self compensation function.Therefore, this liquid crystal mode is also referred to as OCB (optical compensation curved) liquid crystal mode.The advantage of the liquid crystal indicator of curved orientation pattern is that response speed is very fast.

＜IPS pattern 〉

The liquid crystal cells of IPS pattern comprises that write up is at Proc.IDRC (Asia Display ' 95), among pp.577-580 and the pp.707-710 by nematic liquid crystal being applied the system that transverse electric field switches.

＜ecb mode 〉

In the liquid crystal cells of ecb mode, rod shaped liquid crystal molecule substantial horizontal orientation when not applying voltage.Ecb mode is one of liquid crystal display pattern that has simple structure, and write up is in JP-A No.5-203946 for example.

As mentioned above, the present invention can provide a kind of diaphragm of high surface hardness and low moisture permeability, liquid crystal indicator with high surface hardness and the leakage of less light that uses the polaroid of described diaphragm and use described polaroid realized.

Embodiment

Be described more specifically the present invention below with reference to embodiment, but embodiment of the present invention are not limited thereto or are not limited to these embodiment.Unless refer else, all percentages and umber are all by mass.

Use is that cellulose acylate film, low soak layer contain vinylidene chloride polymer and thickness 10 μ m or bigger antiglare layer and as the diaphragm that hard conating (anti-dazzle hard conating) (following be called sometimes anti-dazzle hard coat film) forms the present invention be described as an example by laminated transparent substrates film in regular turn.

＜preparation vinylidene chloride polymer A 〉

In glass-lined voltage-resistant reactor, add 100 parts deionized water, 0.1 part sodium alkyl sulfate and 0.9 part sodium peroxydisulfate, with the system degassing, the temperature with content remains on 50 ℃ then.In another container, mix the vinylidene chloride of 90 quality %, the methacrylonitrile of 5 quality % and the methyl methacrylate of 5 quality %, make monomer mixture.The itaconic acid of 0.6 part methacrylonitrile and 0.8 part is added in the reactor, in 16 hours, adds the monomer mixture of 100 parts of total amounts thereafter continuously.At this moment, 0.1 part sodium bisulfite is added continuously with monomer.Add after the monomer mixtures of whole amounts, begin immediately to reduce interior pressure, react, no longer descend, thereby obtain the aqueous dispersion of vinylidene chloride polymer up to pressure.Stir in the calcium chloride water of the 3 quality % that down 30 aqueous dispersions that restrain vinylidene chloride polymers are added drop-wise at every turn on a small quantity the 100g that has been heated to 60 ℃, wash the agglomerate and the drying of generation thereafter with water, obtain white powder.

The coating fluid that the low soak layer of＜preparation is used 〉

Following composition is added in the mixing channel, stirs each composition of dissolving down, thereby make the coating fluid that low soak layer A-C uses.

[composition of the coating fluid that low soak layer A uses]

12 parts of vinylidene chloride polymer R204

(Saran Resin R204, Asahi Kasei Life ﹠amp; Living Corporation makes)

62 parts of tetrahydrofurans

13 parts of toluene

13 parts of methyl ethyl ketones

[composition of the coating fluid that low soak layer B uses]

12 parts of vinylidene chloride polymer A

62 parts of tetrahydrofurans

13 parts of toluene

13 parts of methyl ethyl ketones

[composition of the coating fluid that low soak layer C uses]

5 parts of vinylidene chloride polymer F216

(Saran Resin F216, Asahi Kasei Life ﹠amp; Living Corporation makes)

9 parts of toluene

18 parts of cyclohexanone

The solubility test of＜vinylidene chloride polymer 〉

Prepare two glass beakers, each beaker contains the 100g cyclohexanone.20g is added in the beaker by the powder of the vinylidene chloride polymer A of above-mentioned preparation, the powder of 36g vinylidene chloride polymer A is added in another beaker, then two beakers are placed 25 ℃ of calibration cells, stirred 60 minutes, detect solubleness.The content that contains the beaker of 20gA dissolves, but the part of content that contains the beaker of 36gA is not dissolved.

Found that from these at 25 ℃, the solubleness of vinylidene chloride polymer A in the 100g cyclohexanone is 20g or bigger extremely less than 36g.

Test vinylidene chloride polymer R204 (Saran Resin R204, Asahi Kasei Life ﹠amp in the mode identical with the powder of vinylidene chloride polymer A; Living makes).The content that contains the beaker of 20g R204 dissolves, but the part of content that contains the beaker of 36g R204 is not dissolved.

Found that from these at 25 ℃, the solubleness of Saran Resin R204 in the 100g cyclohexanone is 20g or bigger extremely less than 36g.

Test vinylidene chloride polymer F216 (Saran Resin F216, Asahi Kasei Life ﹠amp in the mode identical with the powder of vinylidene chloride polymer A; Living Corporation makes).The content that contains the beaker of 20g F216 all dissolves with the content that contains the beaker of 41g F216.

Found that from these at 25 ℃, the solubleness of Saran Resin F216 in the 100g cyclohexanone is 41g or bigger.

The coating fluid that＜preparation hard conating is used 〉

Following composition is added in the mixing channel, stirs each composition of dissolving down, thereby make the coating fluid that anti-dazzle hard conating is used.

[composition of the coating fluid that anti-dazzle hard conating HCL-1 uses]

600.0 parts of UV curable resins (Ltd. makes for PETA, Nippon Kayaku Co.)

184 20.0 parts of Irgacure

(30%) 17.0 part of the toluene dispersion of crosslinked granules of polystyrene

45.0 parts of the crosslinked acrylate of mean grain size 8 μ m-styrene particle

392.0 parts of toluene

98.0 parts of cyclohexanone

0.1 part of silicone oil " X-22-164C "

(embodiment 1)

＜making diaphragm 〉

" coating of low soak layer "

Draw back commercially available cellulose acylate film (Fuji TAC TD80UF, the FUJIFILMCorporation manufacturing of web-like; 1,340mm is wide and 80 μ m are thick) as the transparent substrates film, under transporting velocity 30m/ minute, use excellent spreader to be coated with the coating fluid that above-mentioned low soak layer A uses, and 100 ℃ of dryings 1 minute.When carrying, batch 1,000 meter this product.The thickness of low soak layer is 2.0 μ m.

" coating of hard conating "

To decontrol as the film of the coating of the web-like of support (substrate) with the low soak layer of above-mentioned making, under transporting velocity 15m/ minute, use little gravure roll and scraper to be coated with the coating fluid of anti-dazzle hard conating (HCL-1) usefulness, then 60 ℃ of dryings 150 seconds, with nitrogen wash making oxygen concentration be 1.0vol% or littler following, use 160W/cm air cooling metal halide lamp (Eyegraphics Co. thereafter,, Ltd. make), be 400mW/cm with illumination ²With exposure be 250mJ/cm ²Ultraviolet ray shine solidified coating.Batch the antiglare layer of such formation, obtain having the diaphragm (HCF-1) of anti-dazzle hard conating.The average thickness that solidifies the back antiglare layer is 12.0 μ m.

In the present embodiment, wherein antiglare layer (hard conating) average thickness that is laminated in the curing antiglare layer (hard conating) of the antiglare film on the low soak layer refers to after laminated antiglare layer the thickness that the average thickness of low soak layer is tried to achieve when making up average thickness that low soak layer and antiglare layer obtain and deduct only laminated low soak layer.In addition, determine each thickness by cross section of using the sem observation diaphragm and the mean value of getting 20 arbitrfary points.

(embodiment 2-9, Comparative Examples 2 and 3)

＜making diaphragm 〉

Make anti-dazzle hard coat film HCF-2-HCF-9 and HCF-12 and HCF-13 in the mode identical, except the average thickness of the antiglare layer of solidifying and/or the average thickness of low soak layer are adjusted to the value shown in the table 1 with the anti-dazzle hard coat film HCF-1 of embodiment 1.

(embodiment 10)

＜making diaphragm 〉

Make anti-dazzle hard coat film HCF-10 in the mode identical with the anti-dazzle hard coat film HCF-5 of embodiment 5, the coating fluid that the coating fluid of using except low soak layer is used from low soak layer A becomes the coating fluid that low soak layer B uses, and the average thickness of the antiglare layer of solidifying is adjusted to the value shown in the table 1.

(Comparative Examples 1)

Make anti-dazzle hard coat film HCF-11 in the mode identical with the anti-dazzle hard coat film HCF-1 of embodiment 1, except there not being laminated low soak layer, and the average thickness of antiglare layer is adjusted to 20 μ m.

(Comparative Examples 4 and 5)

Make anti-dazzle hard coat film HCF-14 and HCF-15 in the mode identical with the anti-dazzle hard coat film HCF-1 of embodiment 1, the coating fluid that the coating fluid of using except low soak layer is used from low soak layer A becomes the coating fluid that low soak layer C uses, and the average thickness of the antiglare layer of solidifying is adjusted to the value shown in the table 1.

Use following method (1)-(6) to estimate the anti-dazzle hard coat film HCF-1-HCF-15 that makes above, the results are shown in table 1.

[evaluation of anti-dazzle hard coat film]

(1) specular reflectance

Use spectrophotometer (JASCO manufacturing) to measure the specular reflectance of each anti-dazzle hard coat film sample when incident angle is 5 ° in the 380-780nm wavelength zone.For estimating, use the average reflectance in the 450-650nm wavelength zone.

(2) moisture permeability (moisture permeability under 60 ℃ and 95% relative humidity)

Use be documented in " Physical Properties of Polymer[Koubunshi no Bussei] II " (Polymer Experiment Course[Koubunshi Jikken Kouza] 4, Kyoritsu ShuppanCo., Ltd.), pp.285-294: the method for measuring in the steam transit dose (quality method, thermometer method, vapor method, absorption method) is measured moisture permeability.Each membrane sample of the present invention is cut into diameter 70mm, and conditioning humidity is 24 hours under 60 ℃ and 95% relative humidity, according to JIS Z 0208, uses moisture vapor transmission cup, calculates the amount of moisture (g/m of per unit surface area ²) (moisture permeability={ quality after the conditioning humidity }-{ quality before the conditioning humidity }).The moisture permeability value of contrast cup that does not contain hygroscopic agent is not calibrated.

(3) pencil hardness evaluation

Carry out the pencil hardness evaluation by JIS K 5400 is described, as the index of mar resistance.To optical diffusion film conditioning humidity 2 hours, use JIS S 6006 described 2H-5H test pencils 25 ℃ of temperature and relative humidity 60% time thereafter, under load 4.9N, test, estimate as follows.The maximum hardness that is expressed as " OK " grade is as evaluation of estimate.

OK: estimate 0-1 scratch among the n=5

NG: estimate 3 or more a plurality of scratch among the n=5

(4) thermotolerance evaluation

Each anti-dazzle hard coat film was preserved 3 days at 105 ℃, divided four-stage to estimate its thermotolerance according to following standard.

A: not decolouring

B: almost not decolouring

C: observe some decolourings

D: observe obvious decolouring

(5) no stratum granulosum thickness

Use the antiglare film cross section imaging after scanning electron microscope makes anti-dazzle hard conating laminated, amplify 5,000 times, use the length of cross section microphoto observation, the substrate interface and the particulate of low soak layer are made no stratum granulosum thickness near the distance definition between the part of substrate corresponding to sample Width 10 μ m.This operation repeats 20 times, does not have stratum granulosum thickness in the collection of 20 points, and its mean value is defined as average no stratum granulosum thickness.

(6) fragility

Carry out the axle test according to JIS K 5600-5-1, estimate as follows.

The A:5mm place does not have crackle

B: at the 5mm place crackle is arranged, do not have crackle at the 8mm place

C: crackle is arranged at the 8mm place

From the following as can be seen content of the result of table 1.

Wherein thickness 10 μ m or bigger hard conating are formed on the hard coat film on thickness 0.5 μ m or the bigger low soak layer (being formed by the polyvinylidene chloride resin that has low solubility in cyclohexanone), (moisture permeability is good, is 500g/m to have high surface hardness and low moisture permeability ²It or littler).In this system, the thickness (no stratum granulosum thickness) that does not contain the layer of particle equals the thickness of low soak layer, is 0.3 μ m-3.0 μ m.

On the other hand, wherein thickness 10 μ m or bigger hard conating are formed on the hard coat film on the low soak layer (being formed by the polyvinylidene chloride resin that has high-dissolvability in cyclohexanone), have high surface hardness and 500g/m ²It or bigger moisture permeability can not obtain low fully moisture permeability.

In this system, the thickness (no stratum granulosum thickness) that does not contain the layer of particle increases with respect to the thickness that hangs down soak layer, exceeds the scope of 0.3 μ m-3.0 μ m.

When low soak layer is formed by vinylidene chloride polymer, decolour by heating, but remain on 3.0 μ m or littler by the thickness that will hang down soak layer, this decolouring is minimized.

(making polaroid)

By making polarizing coating on the polyvinyl alcohol film that iodine is adsorbed onto stretching, saponification is handled commercially available visual angle and is enlarged film (Wide View Film SA 12B, FUJIFILM Corporation makes), use poly (vinyl alcohol) binder not fit on the surface of polarizing coating on the surface of laminated liquid crystal layer then.

In addition, the web-like diaphragm HCF-1 that embodiment 1 is made carries out similar saponification processing, uses poly (vinyl alcohol) binder that the surface that does not form coating on it is fitted on another surface of polarizing coating then, thereby makes polaroid P-1.

In addition, make polaroid P-2-P-15, except the diaphragm HCF-1 with web-like becomes HCF-2-HCF-15 in the mode identical with polaroid P-1.

(making liquid crystal indicator)

Peel off the liquid crystal indicator (MRT-191S that uses TN mode liquid crystal unit, the MitsubishiElectric manufacturing) polaroid that is provided with, use bonding agent to replace it to fit on the device respectively polaroid P-1-P-15 of the present invention, make coating in the outside (observation side), and polaroid see through axle and original to fit to seeing through of polaroid on the device spool consistent, thereby make liquid crystal indicator LCD-1-LCD-15.The following characteristic of evaluating liquid crystal device.The results are shown in table 2.

＜phantom evaluation 〉

The fluorescent light with cover that use is exposed (8,000cd/m ²), with 45 ° of each liquid crystal indicators of irradiation, press the following grade evaluation phantom degree that fluorescent light produces when from-45 ° of directions observations from liquid crystal indicator normal to a surface direction towards surface level.

[opinion rating]

A: can not detect the existence of fluorescent light, a speed screen is white in color.

B: can not recognize the profile of fluorescent light at all, but can detect the existence of fluorescent light.

C: the faint profile of seeing fluorescent light, but almost do not have phantom.

D: fluorescent light does not produce phantom, but fuzzy.

E: the fluorescent light phantom is obvious.

Light after＜evaluation high humility is handled leaks (unevenness around estimating) 〉

Liquid crystal indicator was handled 50 hours under 60 ℃ and 90%RH, under 25 ℃ and 60%RH, placed 2 hours then, make liquid crystal indicator provide black display, leak based on the light in following opinion rating visual valuation device front in the darkroom by several observers thereafter.

[opinion rating]

A: do not see that light leaks.

B: the light at edge leaks less than 5mm.

C: the light at edge leaks and is 5mm or bigger extremely less than 10mm.

D: the light at edge leaks and is 10mm or bigger.

Table 2

From the following as can be seen content of the result of table 2.

Light after wherein the antiglare film high humility that fits to the TN mode LCD of outmost surface is handled leaks corresponding with the moisture permeability of antiglare film, and moisture permeability is low more, and light leaks few more.

In addition, in any in being furnished with the liquid crystal indicator LCD-1-LCD-10 of anti-dazzle hard coat film of the present invention, the background phantom is all few, the display quality height.

Not forming the anti-dazzle hard coat film HCF-11 of low soak layer and the thickness of low soak layer is among the anti-dazzle hard coat film HCF-12 of 0.4 μ m, and the moisture permeability height is observed strong light and leaked.

At the thickness of low soak layer is that the thickness of 2.0 μ m and hard conating is among the anti-dazzle hard coat film HCF-13 of 9 μ m, and light leaks few, but can not realize the skin hardness as the object of the invention.

In addition, in being furnished with the liquid crystal indicator LCD-14 and LCD-15 of no stratum granulosum thickness greater than the anti-dazzle hard coat film HCF-14 of 3 μ m and HCF-15, the light scattering on surface increases, and fluorescent light produces phantom, the whole surface of liquid crystal indicator is white in color, and this is unwanted.

Next, will the present invention be described, wherein used thickness 10 μ m or bigger antiglare layer (anti-dazzle hard conating), contained particulate quantitative changeization in the hard conating by the embodiment of diaphragm (anti-dazzle hard coat film).

(embodiment 11-13)

" preparing the coating fluid that anti-dazzle hard conating is used "

By changing the composition of the coating fluid that anti-dazzle hard conating HCL-1 uses among the embodiment 5, make that the amount of crosslinked acrylic acid-styrene particle is the amount shown in the table 3, thereby prepare the coating fluid that anti-dazzle hard conating HCL-2-HCL-4 uses.

" coating of low soak layer "

In the mode identical with the foregoing description 5, draw back web-like commercially available cellulose acylate film (FujiTAC TD80UF, FUJIFILM Corporation makes; 1,340mm is wide and 80 μ m are thick) as the transparent substrates film, under transporting velocity 30m/ minute, use excellent spreader to be coated with the coating fluid that above-mentioned low soak layer A uses, and 100 ℃ of dryings 1 minute.When carrying, batch 1,000 meter this product.The thickness of low soak layer is 1.5 μ m.

" coating of anti-dazzle hard conating "

To decontrol as the film of the coating of the web-like of support (substrate) with the low soak layer of above-mentioned making, under transporting velocity 15m/ minute, use little gravure roll and scraper to be coated with the coating fluid of anti-dazzle hard conating (HCL-2) usefulness, then 60 ℃ of dryings 150 seconds, with nitrogen wash making oxygen concentration be 1.0vol% or littler following, use 160W/cm air cooling metal halide lamp (Eyegraphics Co. thereafter,, Ltd. make), be 400mW/cm with illumination ²With exposure be 250mJ/cm ²Ultraviolet ray shine solidified coating.Batch the antiglare layer of such formation, obtain anti-dazzle hard coat film (HCF-16).The average thickness that solidifies the back antiglare layer is 20 μ m.

With with the identical mode of anti-dazzle hard coat film HCF-16, make anti-dazzle hard coat film HCF-17 and HCF-18 respectively, be used for the coating fluid that anti-dazzle hard conating HCL-3 and HCL-4 use except coating fluid is changed into respectively.

(Comparative Examples 6-9)

With with embodiment 5 and 11-13 in the anti-dazzle hard coat film HCF-5 mode identical of making respectively with HCF-16-HCF-18, make anti-dazzle hard coat film HCF-19-HCF-22 respectively, except the thickness of anti-dazzle hard conating becomes as shown in table 3.

Anti-dazzle hard coat film HCF-5 and HCF-16-HCF-22 by the above-mentioned making of said method (1)-(5) evaluation the results are shown in table 3.

From the following as can be seen content of the result of table 3.

Close in the anti-dazzle hard coat film that is laminated on the low soak layer at anti-dazzle hard conating, when the thickness of anti-dazzle hard conating is 10 μ m or bigger (i.e. 20 μ m),, can reduce moisture permeability by improving the contained grain amount of bonding agent.Consider the situation that pencil hardness tends to reduce when the contained grain amount of bonding agent is 40 parts, grain amount most preferably is 20 parts-35 parts.

On the other hand, when the thickness of anti-dazzle hard conating during less than 10 μ m, pencil hardness is low, and contained grain amount increases, and does not almost observe the effect that moisture permeability is reduced.

Therefore, the preferred thickness of anti-dazzle hard conating is 10 μ m or bigger, and grain amount is 20 parts-35 parts.

Next, film with the anti-dazzle antireflective hard that has low soak layer, antiglare layer and low-index layer structure in regular turn the present invention is described as an example.

(embodiment 14)

" coating of low soak layer "

In the mode identical with the foregoing description 4, draw back web-like commercially available cellulose acylate film (FujiTAC TD80UF, FUJIFILM Corporation makes; 1,340mm is wide and 80 μ m are thick) as the transparent substrates film, under transporting velocity 30m/ minute, use excellent spreader to be coated with the coating fluid that above-mentioned low soak layer A uses, and 100 ℃ of dryings 1 minute.When carrying, batch 1,000 meter this product.The thickness of low soak layer is 1.5 μ m.

" coating fluid that the preparation hard conating is used "

Prepare potpourri from following material: urethane acrylate (100 parts urethane acrylate is made of the Xylene Diisocyanate of pentaerythritol acrylate and hydrogenation); Polyvalent alcohol (methyl) acrylate (49 parts dipentaerythritol acrylate, 24 parts pentaerythritol triacrylate and 41 parts tetramethylol methane tetraacrylate; With (methyl) acrylate copolymer with the alkyl that contains two or more hydroxyls (59 parts have 2-hydroxyethyl and 2, the 3-dihydroxypropyl (methyl) acrylate copolymer; PC 1097, Dainippon Ink ﹠amp; Chemicals, Incorporated makes).Using mixing ratio is 55: 45 butyl acetate and the mixed solvent of ethyl acetate (ethyl acetate account for total solvent 45%), by dilution 1.49), 0.5 part reactive levelling agent (leveling agent) and 5 parts polymerization initiator (Irgacure 184) by the PMMA particle of the mean grain size 8 μ m of 30 parts of total resinous principles of 100 parts above-mentioned mixing (refractive index:, preparation forms the material of hard conating, makes that solid concentration is 55%.Reactive levelling agent is mol ratio 6.3: 1.0: 2.2: the multipolymer of 1.0 dimethyl siloxane, hydroxypropyl siloxane, 6-isocyanates hexyl isocyanuric acid and aliphatic polyester.

" coating of hard conating "

Draw back low soak layer that the usefulness of web-like makes above film, use excellent spreader coating as the coating of support (substrate), and 100 ℃ of heating 1 minute with dry coating.

Use metal halide lamp then, with accumulation light intensity 300mJ/cm ²Ultraviolet ray irradiation film, with solidified coating, form the hard conating of thickness 20 μ m and the anti-dazzle hard coat film (HCF-23) of present embodiment.

(embodiment 15)

Next, anti-reflection layer is laminated on the anti-dazzle hard coat film HCF-23, with the anti-dazzle antireflective hard of making present embodiment film (HCF-24).

" coating fluid that the preparation anti-reflection layer is used "

[coating fluid that preparation anti-reflection layer LNL-1 uses]

At first, it is 500-10 that mean molecular weight (being scaled ethylene glycol) is provided, and (Ltd. makes 000 siloxane oligomer for Colcoat N103, Colcoat Co.; Solids content 2 quality %) as the material that forms anti-reflection layer, measure its number-average molecular weight then.Number-average molecular weight is 950.

In addition, provide number-average molecular weight (being scaled polystyrene) be 5,000 or bigger, as to have fluoroalkyl structure and polysiloxane structure fluorine compounds (Opstar JTA105, JSR Corporation makes; Solids content 5 quality %), measure its number-average molecular weight then.The number-average molecular weight that is scaled polystyrene is 8,000.

(JSR Corporation makes JTA105A; Solids content 5 quality %) as hardening agent.

Next, by mixing 100 parts Opstar JTA105,1 part JTA105A, 590 parts Colcoat N103 and 151.5 parts butyl acetate prepare the coating fluid that anti-reflection layer LNL-1 uses.

" coating of anti-reflection layer "

With the width identical with hard conating, using mould to be coated with the coating fluid that device uses the anti-reflection layer LNL-1 for preparing above is applied on the hard conating of anti-dazzle hard coat film HCF-22, and at 120 ℃ of 3 minutes dryings of heating and solidified coating, form anti-reflection layer (low-refraction layer thickness 0.1 μ m, refractive index 1.43), make the anti-dazzle antireflective hard HCF-24 that films.

(embodiment 16)

Next, be laminated in anti-dazzle antireflective hard that anti-dazzle hard coat film HCF-23 go up the to make present embodiment HCF-25 that films by the anti-reflection layer that will contain hollow particle.

" coating fluid that the preparation anti-reflection layer is used "

[coating fluid that preparation anti-reflection layer LNL-2 uses]

By 100 parts dipentaerythritol acrylate, 15 parts the siloxane polymer with methacryloxypropyl and butyl, 2.5 parts acrylic acid hexanediol ester, 6 parts Lucirin type Photoepolymerizationinitiater initiater, the ultra-fine grain of hollow sphere Si oxide of having used the silane coupling agent with acryloyl group to carry out the diameter 60nm of surface treatment, hydrophobization processing are dispersed in the mixed solvent of IPA, MIBK, butyl cellosolve and toluene (80/9/10.5/0.5); make that solids content is 3%, prepares the coating fluid that anti-reflection layer LNL-2 uses thus.

" coating of anti-reflection layer "

With the width identical with hard conating, using mould to be coated with the coating fluid that device uses the anti-reflection layer LNL-2 for preparing above is applied on the hard conating of anti-dazzle hard coat film HCF-23, and at 120 ℃ of 3 minutes dryings of heating and solidified coating, form anti-reflection layer (low-refraction layer thickness 0.1 μ m, refractive index 1.43), make the anti-dazzle antireflective hard HCF-25 that films.

Anti-dazzle hard coat film HCF-23 that makes above by said method (2), (3), (5) and following method (7) evaluation and anti-dazzle antireflective hard film HCF-24 and HCF-25 the results are shown in table 4.

(7) integrated reflectivity

Use spectrophotometer (JASCO manufacturing) to measure the integrated reflectivity of each anti-dazzle hard coat film sample when incident angle is 5 ° in the 380-780nm wavelength zone.For estimating, use the average reflectance in the 450-650nm wavelength zone.

From the following as can be seen content of the result of table 4.

By laminated anti-reflection layer on anti-dazzle hard coat film, can make have high surface hardness, the anti-dazzle antireflective hard of low moisture permeability and lower integral reflectivity films.

＜making polaroid 〉

By making polarizing coating on the polyvinyl alcohol film that iodine is adsorbed onto stretching, saponification is handled commercially available visual angle and is enlarged film (Wide View Film SA 12B, FUJIFILM Corporation makes), use poly (vinyl alcohol) binder not fit on the surface of polarizing coating on the surface of laminated liquid crystal layer then.

In addition, the web-like diaphragm HCF-23 that embodiment 1 is made carries out similar saponification processing, and the surface of using poly (vinyl alcohol) binder will not form coating then fits on another surface of polarizing coating, thereby makes polaroid P-23.

In addition, make polaroid P-24 and P-25 respectively, except anti-dazzle hard coat film HCF-23 is become HCF-24 and HCF-25 respectively in the mode identical with polaroid P-23.

[making liquid crystal indicator]

Peel off the liquid crystal indicator (MRT-191S that uses TN mode liquid crystal unit, the MitsubishiElectric manufacturing) polaroid that is provided with, use bonding agent to replace it to fit on the device polaroid P-23-P-25 of the present invention respectively, make coating in the outside (observation side), and polaroid see through axle and original to fit to seeing through of polaroid on the device spool consistent, thereby make liquid crystal indicator LCD-23-LCD-25.Estimate in the mode identical with above-mentioned liquid crystal indicator LCD-1-LCD-15.The results are shown in table 5.

Table 5

From the following as can be seen content of the result of table 5.

Wherein film HCF-24 and HCF-25 of the anti-dazzle hard coat film HCF-23 that uses of the present invention and anti-dazzle antireflective hard fits to TN mode LCD LCD-23-LCD-25 on the outmost surface respectively and has few light leak after high humility is handled.

In addition, liquid crystal indicator LCD-23 with anti-dazzle hard coat film of the present invention has few background phantom, especially, have liquid crystal indicator LCD-24 and the LCD-25 that anti-dazzle antireflective hard of the present invention films and have few background phantom and high display quality respectively.

Claims (16)

1. diaphragm, it comprises:

The transparent substrates film;

At lip-deep low soak layer of described transparent substrates film; With

Hard conating on described low soak layer, the average thickness of described hard conating are 10 μ m or bigger,

The moisture permeability of wherein said diaphragm under 60 ℃ and 95% relative humidity is 500g/m ²It or littler.

2. diaphragm as claimed in claim 1, the average thickness of wherein said low soak layer are 0.5 μ m-3.0 μ m.

3. diaphragm as claimed in claim 1, wherein said hard conating comprises particulate, and from the interface between described transparent substrates film and the described low soak layer, that part of average thickness that do not contain particulate is 0.3 μ m-3.0 μ m.

4. diaphragm as claimed in claim 1, the average thickness of wherein said hard conating are 15 μ m or bigger.

5. diaphragm as claimed in claim 1, wherein said low soak layer comprises resin, described resin has the repetitive derived from chloride vinyl monomer.

6. diaphragm as claimed in claim 5, wherein said chloride vinyl monomer is a vinylidene chloride.

7. diaphragm as claimed in claim 5; the wherein said resin that has derived from the repetitive of chloride vinyl monomer is a vinylidene chloride copolymer; described vinylidene chloride copolymer is by can the constituting with the monomer of vinylidene chloride copolymerization of the vinylidene chloride of 88 quality %-93 quality % and 7 quality %-12 quality %, describedly can comprise 40 quality % or more methacrylonitrile with the monomer of vinylidene chloride copolymerization.

8. diaphragm as claimed in claim 5, the wherein said resin that has derived from the repetitive of chloride vinyl monomer is 1g-40g 25 ℃ of solubleness in the 100g cyclohexanone.

9. diaphragm as claimed in claim 1, wherein according to JIS K 5400 described pencil hardness evaluation methods, the pencil hardness under the 4.9N load is 4H or bigger.

10. diaphragm as claimed in claim 1, wherein said hard conating comprise that the ionising radiation solidification compound is as bonding agent.

11. diaphragm as claimed in claim 1, wherein said hard conating comprise the particulate of the 5 quality %-40 quality % that account for bonding agent.

12. diaphragm as claimed in claim 11, wherein the described particulate of at least a portion is a resin particle.

13. diaphragm as claimed in claim 12, the mean grain size of wherein said resin particle are 4 μ m-15 μ m.

14. diaphragm as claimed in claim 1, wherein said transparent substrates film comprises cellulose acylate.

15. a polaroid, it comprises

The polarizer; With

Be located at least one lip-deep diaphragm of the described polarizer,

Wherein said diaphragm comprises:

The transparent substrates film;

At lip-deep low soak layer of described transparent substrates film; With

Hard conating on described low soak layer, the average thickness of described hard conating are 10 μ m or bigger,

The moisture permeability of wherein said diaphragm under 60 ℃ and 95% relative humidity is 500g/m ²It or littler.

16. a liquid crystal indicator, it comprises:

Liquid crystal cells; With

Polaroid, described polaroid comprise the polarizer and be located at least one lip-deep diaphragm of the described polarizer,

Wherein said diaphragm comprises:

The transparent substrates film;

At lip-deep low soak layer of described transparent substrates film; With

Hard conating on described low soak layer, the average thickness of described hard conating are 10 μ m or bigger,

The moisture permeability of wherein said diaphragm under 60 ℃ and 95% relative humidity is 500g/m ²It or littler.